TW202208543A - Dispersion, composite particles, and method for producing composite particles - Google Patents

Abstract

To provide: a dispersion which contains composite particles of a tetrafluoroethylene-based polymer and has excellent dispersion stability; and composite particles which contain a predetermined tetrafluoroethylene-based polymer and silica, have excellent dispersion stability in a dispersion medium, and have desirable physical properties such as high polarity. This dispersion comprises: composite particles that contain an inorganic substance and a tetrafluoroethylene-based polymer having a melting temperature of 260-320 DEG C; an aromatic polymer; and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid dispersion medium, and the dispersion has a viscosity at 25 DEG C of 1,000-100,000 mPa.s.

Description

Dispersion, composite particle, and method for producing composite particle

The present invention relates to a dispersion liquid containing composite particles of a tetrafluoroethylene-based polymer. Moreover, this invention relates to the composite particle containing a specific tetrafluoroethylene type polymer and silica, and its manufacturing method.

Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) are excellent in physical properties such as electrical properties, water and oil repellency, chemical resistance, and heat resistance. In recent years, their particles have been used as printed circuit board materials for high-frequency frequencies. attention. From the viewpoint of improving the flow properties of printed circuit board materials, and improving the electrical properties, fine wiring embeddability, heat resistance, and developability, Patent Document 1 discloses a combination containing silica-coated fluororesin particles and a resin component. thing. As a composite particle of a silica and a tetrafluoroethylene-type polymer, the aspect of patent document 2 or patent document 3 is known. prior art literature Patent Literature

Patent Document 1: International Publication No. 2017/135168 Patent Document 2: Japanese Patent Laid-Open No. 2016-124729 Patent Document 3: International Publication No. 2018/212279 Specification

[Problems to be Solved by Invention]

However, studies by the present inventors have revealed that the resin composition described in Patent Document 1 has insufficient uniformity and dispersion stability when dissolved or dispersed in a liquid, and thus has problems in its use. In addition, with regard to the molded product obtained from the dispersion liquid, the uniformity of the component distribution tends to decrease, and the appearance of the molded product tends to be roughened. Furthermore, with regard to epoxy resins, maleimide compounds, cyanate compounds, benzodiazepine compounds, etc., which are specifically disclosed in Patent Document 1 as usable resin components, these are polymerized with tetrafluoroethylene. There is still room for improvement in the processability of the composition of the product and the heat resistance of the obtained molded product. On the other hand, tetrafluoroethylene-based polymers have extremely low polarity and low affinity with other components, so it is also difficult to highly interact with silica. Therefore, it is difficult to incorporate a sufficient amount of silica into the composite particles of Patent Document 2 or Patent Document 3. In addition, the composite particles of the above-mentioned documents have low interaction between silica and the tetrafluoroethylene-based polymer, so that the stability of the composite particles themselves is not sufficient, and the silica is easily detached from the composite particles. Therefore, it is necessary to ensure the interaction between the silica and the tetrafluoroethylene-based polymer, and the selection range of silica (the amount of hydroxyl groups of silica, etc.) is easily limited. Furthermore, due to this limitation, the use of the composite particles of the above-mentioned documents is limited. For example, it is difficult to improve the affinity of the composite particles with a liquid medium, and when preparing a liquid composition in which the composite particles are dispersed, foaming is severe, and it is also difficult to ensure the dispersion stability.

The inventors of the present invention have made intensive studies and, as a result, have obtained the knowledge that the composite particles containing a specific tetrafluoroethylene-based polymer and an inorganic substance, an aromatic polymer, and a liquid dispersion medium are dispersed in the liquid dispersion medium. The dispersion liquid in a specific viscosity range has excellent dispersion stability. In addition, it was found that the molded product obtained from the dispersion liquid is relatively dense, and is particularly excellent in a low linear expansion coefficient and the like. Furthermore, the inventors of the present invention have obtained the knowledge that composite particles containing a specific tetrafluoroethylene-based polymer and an inorganic substance are contained, and a liquid dispersion medium comprising two types of liquid dispersion media having different boiling points, and the two A dispersion in which the liquid dispersion medium is in a relationship of forming an azeotrope has excellent dispersion stability, and the molded product obtained from the dispersion is relatively dense, and has excellent characteristics such as low coefficient of linear expansion represented by appearance. Furthermore, the inventors of the present invention have found that the above-mentioned problems can be solved by using a specific tetrafluoroethylene-based polymer to control the atomic ratio of fluorine and silicon on the surface of the obtained composite particles. An object of the present invention is to provide a dispersion liquid having excellent dispersion stability. Moreover, the objective of this invention is to provide the dispersion liquid which can obtain the compact which is excellent in characteristics, such as a low linear expansion coefficient represented by an external appearance. Another object of the present invention is to provide composite particles which are excellent in dispersion stability in a dispersion medium and have desired physical properties such as high polarity, and a method for producing the composite particles. [Technical solutions to problems]

The present invention has the following aspects. <1> A dispersion containing composite particles comprising a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an inorganic substance, an aromatic polymer, and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid In the dispersion medium, the viscosity of the above dispersion liquid at 25°C is 1,000 to 100,000 mPa·s. <2> The dispersion liquid according to <1>, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a perfluoro(alkyl vinyl ether)-based unit and having a polar functional group; or a relative A tetrafluoroethylene-based polymer that contains 2.0-5.0 mol % of perfluoro(alkyl vinyl ether)-based units in the total unit and does not have a polar functional group. <3> The dispersion liquid according to <1> or <2>, wherein the inorganic substance is silica. <4> The dispersion liquid according to any one of <1> to <3>, wherein the content of the aromatic polymer is less than the content of the composite particles. <5> The dispersion liquid according to any one of <1> to <4>, wherein the aromatic polymer is selected from the group consisting of aromatic polyimide, aromatic polyimide, aromatic polyimide, At least one of the group consisting of polyphenylene ether, liquid crystal polyester, and aromatic maleimide. <6> A dispersion liquid comprising composite particles comprising a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an inorganic substance, and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid dispersion medium, and the above The liquid dispersion medium includes two liquid dispersion media having different boiling points, and the two liquid dispersion media are in a relationship of forming an azeotrope. <7> The dispersion liquid according to <6>, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a perfluoro(alkyl vinyl ether)-based unit and having a polar functional group; or a relative A tetrafluoroethylene-based polymer that contains 2.0-5.0 mol % of perfluoro(alkyl vinyl ether)-based units in the total unit and does not have a polar functional group. <8> The dispersion liquid according to <6> or <7>, wherein the mixing ratio of the high-boiling point dispersion medium in the above-mentioned two liquid dispersion media with different boiling points is more than that in the azeotropic mixture of the above-mentioned two liquid dispersion mediums The composition ratio (mass ratio) of the high boiling point dispersion medium. <9> The dispersion liquid according to any one of <6> to <8>, wherein at least one of the two liquid dispersion media having different boiling points constituting the liquid dispersion medium is water, alcohol or amide. <10> A composite particle containing a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and containing 1 to 5 mol % of perfluoro(alkyl vinyl ether)-based units with respect to the total units, and For silica, the amount of silicon atoms in the surface of the composite particles measured by X-ray photoelectron spectroscopy is 1 or more relative to the amount of fluorine atoms. <11> The composite particles according to <10>, wherein the average particle diameter is 2 μm or more and 10 μm or less. <12> The composite particles according to <10> or <11>, wherein the amount of the silica is 15 to 85 parts by mass relative to 100 parts by mass of the tetrafluoroethylene-based polymer. <13> The composite particle according to any one of <10> to <12>, which has the above-mentioned tetrafluoroethylene-based polymer as a core, and has the above-mentioned silica on the surface of the above-mentioned core. <14> The composite particle according to any one of <10> to <13>, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having a polar functional group. <15> A method for producing a composite particle, wherein the composite particle is the composite particle according to any one of <10> to <14>, wherein the method for producing the composite particle comprises the above-mentioned tetrafluoroethylene-based polymer particle and the above-mentioned two. The above-mentioned composite particles are obtained by colliding with silicon oxide in a suspended state at a temperature equal to or higher than the melting temperature of the above-mentioned tetrafluoroethylene-based polymer. [Effect of invention]

According to the present invention, a dispersion liquid of a tetrafluoroethylene-based polymer excellent in dispersion stability can be obtained. The molded product formed from the dispersion liquid of the present invention is relatively dense and excellent in physical properties such as appearance, heat resistance, electrical properties, and low linear expansion, and can be used, for example, as a constituent material of printed circuit boards. According to the present invention, it is possible to provide composite particles which are excellent in dispersion stability in a dispersion medium and have desired physical properties such as high polarity, and a method for producing the same. When the dispersion liquid containing the above-mentioned composite particles is applied to a substrate, the appearance of the coating film is excellent. Furthermore, from the above dispersion liquid, a laminate and a film having excellent properties (electrical properties, low linear expansion, etc.) based on a tetrafluoroethylene-based polymer and an inorganic substance, especially silica, can be obtained.

The following terms have the following meanings. "Average particle diameter (D50)" is the volume-based cumulative 50% diameter of the object (particle) determined by the laser diffraction scattering method. That is, the particle size distribution of the object is measured by the laser diffraction scattering method, and the cumulative curve is obtained by taking the total volume of the particles of the object as 100%, and the above-mentioned "average particle size (D50)" is the cumulative curve The particle size at the point where the cumulative volume reaches 50%. "D90" is the volume-based cumulative 90% diameter of the object measured in the same manner as above. The D50 and D90 of the object (particles) were obtained by dispersing the particles in water and using a laser diffraction scattering particle size distribution analyzer (manufactured by Horiba, Ltd., LA-920 measuring device) ) was analyzed by the laser diffraction scattering method. "Melting temperature (melting point)" is the temperature corresponding to the maximum value of the melting peak of the polymer measured by differential scanning calorimetry (DSC). The "glass transition point (Tg)" is a value determined by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method. "Viscosity" is a value obtained by measuring the object (dispersion liquid or liquid composition) at 25°C under the condition of a rotational speed of 30 rpm using a Brookfield viscometer. The measurement was repeated three times, and the average value of the three measurements was used. The "thixotropy ratio" is a value (η ₁ /η ₂ ) calculated by measuring the object (dispersion or liquid composition) at a rotational speed of 30 rpm. The value (η ₁ /η ₂ ) was calculated by dividing the viscosity η ₁ by the viscosity η ₂ obtained by the measurement at a rotational speed of 60 rpm. The measurement of each viscosity was repeated 3 times, and the average value of the measured values of the 3 times was calculated. The "specific surface area" is a value calculated by measuring particles by the gas adsorption (constant volume method) BET multipoint method, and was calculated using NOVA4200e (manufactured by Quantachrome Instruments). The "unit" in the polymer may be an atomic group directly formed from a monomer, or an atomic group in which a part of the structure is converted by treating the obtained polymer by a specific method. The unit based on the monomer A contained in the polymer is also simply referred to as "monomer A unit".

The first dispersion liquid of the present invention (hereinafter also referred to as "the present dispersion liquid A") contains: composite particles (hereinafter also referred to as "the present particles") containing tetrafluoroethylene-based polymerization with a melting temperature of 260 to 320°C (hereinafter also referred to as "F polymer") and inorganic substances; aromatic polymers; and liquid dispersion medium. The dispersion liquid A is a dispersion liquid in which the particles are dispersed in a liquid dispersion medium, and the viscosity at 25°C is 1000-100000 mPa·s.

This dispersion liquid A is excellent in dispersion stability. The reason why the dispersion stability of the present dispersion liquid A is improved, and the correlation between the composition of the present particles contained in the present dispersion liquid A and the dispersion stability, and the mechanism of action are not certain, but are presumed, for example, as follows. The wettability of particles containing inorganic substances is greatly improved. When the above-mentioned particles with improved wettability are added to a liquid dispersion medium, they tend to become a smooth suspension in which the particles are easily precipitated, rather than a dispersion. On the other hand, this particle contains the F polymer and an inorganic substance. Compared with non-thermofusible tetrafluoroethylene-based polymers, F polymer not only has excellent shape stability such as fibrillation resistance, but also has a configuration with a higher degree of freedom in which the restriction of molecular motion is alleviated at the single-molecule level. . The above-mentioned F polymer tends to form microscopic spherulites at the level of molecular aggregates, and therefore microscopic uneven structures tend to be formed on the surface thereof, thereby tending to increase the surface area. Therefore, it is considered that the molecular aggregate of the F polymer can form the present particle by being able to stably and physically adhere closely to the inorganic substance without losing its shape. In addition, although the surface energy of the F polymer is low and the dispersion stability is low, the present particle formed by the combination of the F polymer and the inorganic substance is more likely to interact with other present particles and the liquid dispersion medium than the F polymer, thereby It is considered to be excellent in dispersion stability. Furthermore, it is considered that, by coexisting in the liquid dispersion medium an aromatic polymer having a hydrophobicity like the F polymer and having a high affinity with the F polymer, higher dispersion stability, higher viscosity, and better tactility can be obtained. The dispersion liquid A has excellent dispersion liquid properties such as transformation ratio and sedimentation rate, and is excellent in handleability. As a result, it is considered that the following molded article can be formed from the present dispersion A. The molded article highly possesses the physical properties of the F polymer, the physical properties of the inorganic material, and the physical properties of the aromatic polymer, and the composition uniformity is high and relatively dense (with relatively small voids), and excellent electrical properties.

In the present invention, the F polymer constituting the present particle is a hot-melt polymer including a unit (TFE unit) based on tetrafluoroethylene (TFE). The melting temperature of the F polymer is 260-320°C, preferably 280-320°C, more preferably 285-320°C. In the above case, the heat resistance of the molded product formed from the dispersion liquid A becomes excellent. Here, the term "hot-melt polymer" means a polymer having a melt flow rate of 1 to 1000 g/10 minutes at a temperature under a load of 49 N. The glass transition point of the F polymer is preferably 75 to 125°C, more preferably 80 to 100°C. Examples of the F polymer include a polymer (PFA) containing a TFE unit and a unit based on perfluoro(alkyl vinyl ether) (PAVE) (PAVE unit), and a unit containing a TFE unit and a unit based on hexafluoropropylene (HFP). The polymer (FEP), preferably PFA. As PAVE, CF ₂ =CFOCF ₃ , CF ₂ =CFOCF ₂ CF ₃ , and CF ₂ =CFOCF ₂ CF ₂ CF ₃ (PPVE) are preferred, and PPVE is more preferred. The melt viscosity of the F polymer at 380°C is preferably 1×10 ² to 1×10 ⁶ Pa·s, more preferably 1×10 ³ to 1×10 ⁶ Pa·s. If the melting temperature, glass transition point or melt viscosity of the F polymer is within the above-mentioned ranges, the above-mentioned action mechanism is easily strengthened.

As a preferred aspect of the F polymer, preferred are: polymer (1), which contains TFE unit and PAVE unit, and has polar functional groups; or polymer (2), which contains TFE unit and PAVE unit, relative to It contains 2.0-5.0 mol % of PAVE units in the total monomer units, and does not have polar functional groups; it is more preferably polymer (1). These F polymers are not only excellent in the dispersion stability of the present particles, but also tend to be more densely and homogeneously distributed in molded articles such as polymer layers obtained from the present dispersion A. Moreover, when the dispersion liquid containing these F polymers is coated on a substrate to form a polymer layer, microscopic spherulites are easily formed in the polymer layer, and the adhesion with other components is easily improved. As a result, a molded product excellent in various physical properties such as electrical properties can be more easily obtained.

The polar functional group possessed by the polymer (1) may be contained in the unit contained in the polymer or in the terminal group of the main chain of the polymer, preferably contained in the unit contained in the polymer. As the latter polymer, polymers having polar functional groups as terminal groups derived from polymerization initiators, chain transfer agents, radiation treatment, etc.; or polymers having polar functional groups prepared by plasma treatment or ionizing radiation treatment can be exemplified base polymer.

The number of polar functional groups in the polymer (1) is preferably 10 to 5000, more preferably 100 to 3000 per 1×10 ⁶ of carbon atoms in the main chain. In addition, the amount of the oxygen-containing polar group in the polymer (1) can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133. The polar functional group is preferably a hydroxyl group-containing group, a carbonyl group-containing group and a phosphonic acid group-containing group. In order to easily improve the physical properties such as the dispersibility of the particles, a hydroxyl group-containing group and a carbonyl group-containing group are more preferable. Furthermore, a carbonyl group-containing group is preferable.

The hydroxyl group-containing group is preferably an alcoholic hydroxyl group-containing group, more preferably -CF ₂ CH ₂ OH, -C(CF ₃ ) ₂ OH and 1,2-ethylene glycol (-CH(OH) CH ₂ OH). The carbonyl group-containing group is preferably a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a urethane group (-OC(O)NH ₂ ), an acid anhydride residue (-C(O)OC) (O)-), imide residues (-C(O)NHC(O)- etc.) and carbonate groups (-OC(O)O-), more preferably acid anhydride residues.

The polymer (1) is preferably a polymer comprising a TFE unit, a PAVE unit, and a unit based on a monomer having a polar functional group, and more preferably, with respect to the total units, in the order of these units, 90 to 99 moles. Ear%, 0.5-9.97 mol%, 0.01-3 mol% polymer. When a polar functional group exists, the affinity or adhesiveness with an inorganic substance is further improved, and it is preferable from this point. As for the monomer with polar functional group, it is preferably itaconic anhydride, citraconic anhydride or 5-norene-2,3-dicarboxylic anhydride (alias: bicycloheptenedicarboxylic anhydride; hereinafter also referred to as "NAH" ). Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.

The polymer (2) is composed of only TFE units and PAVE units, and preferably contains 95.0 to 98.0 mol % of TFE units and 2.0 to 5.0 mol % of PAVE units with respect to the total units. The content of the PAVE units in the polymer (2) is preferably 2.1 mol % or more, more preferably 2.2 mol % or more, based on the total units. The above-mentioned polymer has a higher degree of freedom in molecular configuration, and the above-mentioned action mechanism is easily strengthened. Furthermore, the fact that the polymer (2) does not have polar functional groups means that the number of polar functional groups contained in the polymer is less than 500 per 1×10 ⁶ carbon atoms constituting the main chain of the polymer. The number of the above-mentioned polar functional groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of the above-mentioned polar functional groups is usually zero.

The polymer (2) can be produced by using a polymerization initiator or a chain transfer agent that does not generate polar functional groups as the terminal groups of the polymer chain, and can also be used for polymers with polar functional groups (at the terminal groups of the polymer chain). A polymer having a polar functional group derived from a polymerization initiator, etc.) is produced by fluorination treatment. As a method of the fluorination treatment, a method using fluorine gas (refer to Japanese Patent Laid-Open No. 2019-194314, etc.) can be mentioned.

In the present invention, the shape of the inorganic substances constituting the particles is preferably particles. Examples of inorganic substances include particles containing oxides, nitrides, elemental metals, alloys, and carbon, preferably silicates (silicon oxide (silicon dioxide), wollastonite, talc, mica), metal oxides (oxide particles of beryllium, cerium oxide, aluminum oxide, alkali aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc.), boron nitride and magnesium metasilicate (mass talc), preferably containing particles selected from the group consisting of aluminum, magnesium, silicon, Particles of inorganic oxides of at least one of the elements of titanium and zinc, more preferably particles of silicon dioxide, titanium oxide, zinc oxide, talc and boron nitride, and particularly preferably particles of silicon dioxide. In addition, the inorganic substance may be ceramics. One type of inorganic substances may be used, or two or more types may be mixed and used. When two or more inorganic substances are mixed and used, two kinds of silica particles may be mixed and used, or silica particles and metal oxide particles may be mixed and used.

The average particle diameter (D50) of the inorganic particles is preferably 20 μm or less, more preferably 5 μm or less. The average particle diameter is preferably 0.001 μm or more, more preferably 0.01 μm or more. The specific surface area (BET method) of the inorganic particles is preferably 1 to 20 m ² /g, more preferably 5 to 8 m ² /g. In this case, the interaction between the inorganic substance and the F polymer is easily strengthened. In addition, in the molded product (polymer layer, etc.), the inorganic substance and the F polymer are more uniformly distributed, and the physical properties of both are easily expressed at a higher level.

The interaction between the above-mentioned inorganic substance and the F polymer is easily strengthened, and the dispersion stability of the present dispersion liquid A is easily further improved. Moreover, about the molded object (for example, the following polymer layer and film) formed from this dispersion liquid A, the physical property based on an inorganic substance is easy to express remarkably.

Among them, the dispersion liquid A preferably contains silica as the inorganic substance. The content of silica in the inorganic substance is preferably 80% by mass or more, more preferably 90% by mass or more. The upper limit of the content of silica is 100% by mass.

It is preferable that at least a part of the surface of the said inorganic substance is surface-treated. As the surface treatment agent used for the above surface treatment, polyhydric alcohols (trimethylolethane, pentaerythritol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkanolamines, Amines (trimethylamine, triethylamine, etc.), paraffin, silane coupling agents, silicones, polysiloxanes, oxides of aluminum, silicon, zirconium, tin, titanium, antimony, etc., their hydroxides, and the like The hydrated oxides, their phosphates. As the silane coupling agent, preferred are: 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethyl oxysilane, 3-methacryloyloxypropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane.

Specific examples of inorganic substances include silicon dioxide ("Admafine (registered trademark)" series manufactured by Admatechs, etc.), zinc oxide (Sakai Chemical Industry Co., Ltd.) surface-treated with esters such as propylene glycol diddecanoate (Sakai Chemical Industry Co., Ltd.) manufactured "FINEX (registered trademark)" series, etc.), spherical fused silica ("SFP (registered trademark)" series manufactured by DENKA, etc.), and rutile titanium dioxide ( "Tipaque (registered trademark)" series manufactured by Ishihara Sangyo Co., Ltd.), rutile-type titanium dioxide surface-treated with alkylsilane ("JMT (registered trademark)" series manufactured by Imperial Chemical Co., Ltd., etc.), hollow-shaped titanium dioxide Silicon ("E-SPHERES" series manufactured by Pacific Cement Corporation, "SiliNax" series manufactured by Nippon Steel Mining Corporation, "Ecco sphere" series manufactured by Emerson & Cuming Corporation, hydrophobic AEROSIL series "RX200" manufactured by Japan Aerosil Corporation) etc.), talc (“SG” series manufactured by NIPPON TALC, etc.), block talc (“BST” series manufactured by NIPPON TALC, etc.), boron nitride (“UHP” series manufactured by Showa Denko, etc.) "Denka Boron Nitride" series ("GP", "HGP" grades), etc.).

The shape of the inorganic particles includes granular, needle-like (fibrous), and plate-like shapes, and specifically, spherical, scaly, lamellar, leaf-like, almond-like, columnar, cockscomb, equiaxed Shape, leaf shape, mica shape, block shape, plate shape, wedge shape, rosette shape, net shape, angular column shape. Among them, spherical shape and scaly shape are preferable, and spherical shape is more preferable.

The spherical inorganic particles are preferably substantially spherical. The substantially spherical shape means that the ratio of spherical particles having a ratio of a short axis to a long diameter of 0.5 or more is 95% or more when observed with a scanning electron microscope (SEM). In the substantially spherical inorganic particles, the ratio of the short axis to the long axis is preferably 0.6 or more, more preferably 0.8 or more. The above-mentioned comparison is preferably less than 1. When such substantially spherical inorganic particles are used, the inorganic material and the F polymer are more uniformly distributed in the molded product (polymer layer, etc.), and the physical properties of both are likely to be more highly expressed.

The aspect ratio of the scaly inorganic particles is preferably 5 or more, more preferably 10 or more. The aspect ratio is preferably 1000 or less.

Examples of the aspect of the particle present in the present dispersion liquid A include: the aspect in which the F polymer is used as the core, and the inorganic substance is attached to the surface of the core (hereinafter also referred to as "Aspect I"); The inorganic substance serves as the core, and the F polymer adheres to the surface of the core (hereinafter also referred to as "Aspect II"). Here, "core" means the core (center part) required for forming the particle shape of the composite particle, and does not mean the main component in the composition of the composite particle. The attachment (inorganic matter or F polymer) attached to the surface of the core may be attached to only a part of the surface of the core, or may be attached to most or the entire surface of the core. In the former case, the attachment can also be said to be in a state in which it adheres to the surface of the nucleus in a dusty state, in other words, in a state in which most of the surface of the nucleus is exposed. In the latter case, the attachment can also be said to be in a state of spreading over the surface of the core or a state of covering the surface of the core, and the composite particle can also be said to have a core-shell structure including a core and a shell covering the core.

The present particle is preferably in aspect I, and preferably in the aspect in which the F polymer and the inorganic substance are in the form of particles, respectively. In this case, in the present particle, the inorganic substance having higher hardness and higher dispersion stability than the F polymer is exposed on the surface. As a result, the F polymer is not easily modified, and the fluidity and handleability of the particles are easily improved. Moreover, the dispersion stability of this particle|grains becomes high easily.

Hereinafter, the particulate F polymer is also referred to as "F particle", and the present particle of Aspect I will be described. The core of the F polymer may include a single F particle, or may include a collection of F particles. In the present particle of Aspect I, it is preferable to set the D50 of the core of the F polymer to be larger than the D50 of the inorganic particle, and to set the amount of the F polymer in the present particle to be larger than the amount of the inorganic substance.

In the present particle of aspect I, the D50 of the inorganic particle is preferably 0.001 to 0.5, more preferably 0.01 to 0.3, based on the D50 of the core of the F polymer. Specifically, it is preferable that the D50 of the core of the F polymer exceeds 1 μm and the D50 of the inorganic particle is 0.1 μm or less. Moreover, 0.1 mass part or more is preferable with respect to 100 mass parts of F polymers, and, as for the quantity of an inorganic substance particle, 1 mass part or more is more preferable. The upper limit is preferably 50 parts by mass, more preferably 25 parts by mass, and still more preferably 5 parts by mass. In the present particle of Aspect I thus obtained, the above relationship is maintained, so that the D50 of the core of the F polymer is greater than the D50 of the inorganic particle, and the F polymer occupies more mass than the inorganic substance. In this case, the surface of the core of the F polymer is covered with a larger amount of inorganic particles, so that the particle has a core-shell structure. Moreover, in this case, the aggregation of F particles is suppressed, and it is easy to obtain the present particle in which the inorganic particles are adhered to the core including the individual F particles.

The inorganic particles are preferably spherical, and more preferably substantially spherical particles. In this case, the dispersibility stability of the present particle obtained tends to be high. In the substantially spherical inorganic particles, the ratio of the short axis to the long axis is preferably 0.5 or more, more preferably 0.8 or more. The above-mentioned comparison is preferably less than 1. Here, "spherical" includes not only a real ball but also a slightly deformed ball. When such substantially spherical inorganic particles are used, the inorganic material and the F polymer are more uniformly distributed in the molded product (polymer layer, etc.), and the physical properties of both can be easily expressed at a higher level. Inorganic particles can also be embedded in the core of the F polymer.

In the present particle of aspect I, the D50 of the inorganic particle is preferably in the range of 0.001 to 0.3 μm, more preferably 0.005 to 0.2 μm, and still more preferably 0.01 to 0.1 μm. When D50 exists in this range, the handleability and fluidity of this particle|grains are easy to improve, and the dispersion stability of this dispersion liquid A is easy to become high. In addition, the particle size distribution of the inorganic particles uses the value of D90/D10 as an index, and is preferably 3 or less, more preferably 2.9 or less. Here, "D10" is the volume-based cumulative 10% diameter of the object measured in the same manner as D50 and D90. In this case, it is easy to control the fluidity of the present particles obtained.

It is preferable that at least a part of the surface of the inorganic particle is surface-treated, and it is more preferable that it is surface-treated with a silazane compound such as hexamethyldisilazane, a silane coupling agent, or the like. As a silane coupling agent, the above-mentioned compound is mentioned. One type of inorganic particles may be used, or two or more types may be mixed and used. When two kinds of inorganic particles are mixed and used, the average particle diameter of each inorganic particle can be different from each other, and the content ratio (mass ratio) of each inorganic particle can be appropriately set according to the required function.

In the present particle of Aspect I, the D50 of the core of the F polymer is preferably 0.1 μm or more, more preferably more than 1 μm. The upper limit is preferably 100 μm, more preferably 50 μm, and still more preferably 10 μm. Moreover, 50-99 mass % is preferable, and, as for the ratio of the F polymer in the present particle of Aspect I, it is more preferable that it is 75-99 mass %. 1-50 mass % is preferable, and, as for the ratio of an inorganic substance, 1-25 mass % is more preferable.

The present particle of Aspect I may be further surface-treated according to the physical properties of the inorganic substances attached to the surface. As a specific example of this surface treatment, the following method is mentioned which surface-treats the particle|grains of Aspect I with siloxanes, such as polydimethylsiloxane, or a silane coupling agent. The above-mentioned surface treatment can be performed by mixing the dispersion liquid in which the present particles are dispersed with a siloxane or a silane coupling agent, and reacting the siloxane or the silane coupling agent to recover the present particles. As a silane coupling agent, the silane coupling agent which has the above-mentioned functional group is preferable. According to the above method, the surface properties of the present particle can be further adjusted.

Hereinafter, the present particle of aspect II will be described. In the present particle of aspect II, the F polymer may be in the form of particles or non-particulate. Preferably, at least a portion of the F polymer is fused to the inorganic core. In the present particle of aspect II, the D50 of the inorganic core is preferably 1 μm or more, more preferably more than 3 μm. The upper limit thereof is preferably 40 μm, more preferably 30 μm. In the present particle of Aspect II, when the F polymer is in the form of particles, the D50 of the F particle is preferably in the range of 0.1 to 10 μm, more preferably 1 to 5 μm. When D50 exists in this range, the handleability and fluidity|liquidity of this particle|grains are easy to improve, and dispersion stability is easy to become high. Moreover, 50-99 mass % is preferable, and, as for the ratio which an inorganic substance occupies in the present particle of Aspect II, it is more preferable that it is 60-90 mass %. The ratio of the F polymer is preferably from 1 to 50 mass %, more preferably from 10 to 40 mass %.

D50 of this particle is preferably 30 μm or less, more preferably 20 μm or less. D50 of this particle is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 3 μm or more. Moreover, D90 of this particle is preferably 30 μm or less, more preferably 20 μm or less. When D50 and D90 of the present particle are within the above-mentioned ranges, the dispersion stability of the present particle in the present dispersion A and the physical properties of the molded product (polymer layer, etc.) obtained from the present dispersion A are likely to be further improved.

The present particles are preferably produced by the following method: a method of colliding F particles with inorganic particles in a suspended state at a temperature higher than the melting temperature of the F polymer (hereinafter also referred to as "dry method A"); pressing Or a method of colliding F particles with inorganic particles in a sheared state (hereinafter also referred to as "dry method B"). Alternatively, it can also be produced by a method such as shearing a liquid composition containing F particles and inorganic particles to solidify the F particles (hereinafter also referred to as "wet method").

In the dry method A, for example, the F particles and the inorganic particles are supplied in a high-temperature turbulent atmosphere, and stress is applied to them by collision between the F particles and the inorganic particles to form a complex. This dry method A is sometimes referred to as hybrid treatment. The atmosphere is formed by gas. As the gas that can be used, air, oxygen, nitrogen, argon, or a mixed gas thereof can be exemplified. The F particles and the inorganic particles may be supplied to the atmosphere at one time as a pre-mixed mixture, or they may be separately supplied to the atmosphere.

When the F particles and the inorganic particles are supplied in a high-temperature atmosphere, it is preferable that the particles are in a state in which they do not agglomerate with each other. As this method, a method of suspending particles in a medium (gas or liquid) can be used. Furthermore, a mixture of gas and liquid can be used as the medium. In the dry method A, after preparing a high-temperature turbulent atmosphere, F particles and inorganic particles may be supplied therein, or after suspending the F particles and inorganic particles in a medium, the medium may be heated to form a high-temperature turbulent atmosphere. flow atmosphere. As a device that can be used for the former, for example, a device in which the particles are sandwiched between the inner wall of the container and the agitator while the particles are agitated by a high-speed rotating agitator such as a stirring blade in a cylindrical container can be mentioned. As for stress application, the above-mentioned device includes, for example, "Hybridization System" (registered trademark) manufactured by Nara Machinery Manufacturing Co., Ltd. The temperature of the atmosphere is preferably 80°C or higher, more preferably 110°C or higher. The temperature of the atmosphere is preferably 400°C or lower, more preferably 200°C or lower, and still more preferably 120°C or lower. In the case of the dry method A, the D50 of the F particles and the silica particles can be used in the above-mentioned range, and they can be collided in a suspended state at a temperature above the melting temperature of the F polymer. It is preferable to make 15-85 mass parts of silica collide with the F polymer in a suspended state at a temperature higher than the melting temperature of the F polymer with respect to 100 mass parts of the F polymer. Furthermore, when the inorganic particles contain a large amount of aggregates formed by agglomerating primary particles thereof, the aggregates can be crushed before being supplied to a high-temperature atmosphere. As the method for crushing the aggregate, a method using a jet mill, a pin mill, and a hammer mill is exemplified.

In the dry method B, for example, the F particles and inorganic particles are pressed against the inner peripheral surface (receiving surface) of the cylindrical rotating body rotating around the central axis by centrifugal force, and the inner peripheral surface is separated by a small distance. The cooperation of the internal components gives the above-mentioned particles a pressing force or a shearing force to combine them. This dry process B is sometimes referred to as a mechanofusion process. The atmosphere in the cylindrical rotating body can be an inert gas atmosphere or a reducing gas atmosphere. The temperature of the atmosphere is preferably below the melting temperature of the F polymer, more preferably 100°C or below. The distance between the inner peripheral surface of the cylindrical rotating body and the internal member is appropriately set according to the average particle diameter of the F particles and the inorganic particles. The separation distance is usually preferably 1 to 10 mm. The rotational speed of the cylindrical rotating body is preferably 500-10000 rpm. In this case, it is easy to improve the production efficiency of the particles. Furthermore, when the inorganic particles contain a large amount of aggregates formed by agglomerating primary particles thereof, the aggregates may be crushed in the same manner as described in the above-mentioned dry method A before being supplied to the cylindrical rotating body.

Dry method B can also be carried out using a pulverizing and mixing apparatus (for example, "Nobilta" (registered trademark) manufactured by Hosokawa Micron Co., Ltd.), which is provided with a rotating tank arranged so that the rotating shaft is in a horizontal direction, and has A pulverizing and mixing chamber having an elliptical (special-shaped) cross-section; and a pulverizing and mixing blade rotatably inserted into the pulverizing and mixing chamber of the rotating tank so that the rotating shaft is disposed at a position concentric with the rotating axis of the rotating tank, and has an ellipse Shaped (shaped) section. In this pulverizing and mixing device, the F particles and the inorganic particles are pressed between the short-diameter portion of the pulverizing and mixing chamber and the long-diameter portion of the pulverizing and mixing blade, and the particles are compounded by applying a pressing force or a shearing force. Furthermore, in the pulverizing and mixing device, the rotation direction of the rotating tank and the rotating direction of the pulverizing and mixing blades are preferably opposite, and the rotation speed of the rotating tank is preferably set to be slower than the rotation speed of the pulverizing and mixing blades. According to this pulverizing and mixing device, the pulverizing and mixing chamber and the pulverizing and mixing blades can be formed into irregular cross-sections, and instantaneous pressing force or shearing force is repeatedly applied to the F particles and inorganic particles that flow under their own weight in the pulverizing and mixing chamber. Therefore, the particles described above can be pulverized and mixed in a short period of time while reducing adverse effects caused by heat, so that the present particles having the desired properties can be easily obtained.

The wet method is a method of, for example, stirring a liquid composition containing F particles and inorganic particles, destabilizing it by shearing, causing it to solidify, and combining the F particles and the inorganic particles, thereby obtaining the present invention. particle. When the inorganic particles are silica, colloidal silica is suitably used.

In the wet method, the total content of the F particles and the inorganic particles in the liquid composition is preferably 30% by mass or more, more preferably 40 to 80% by mass with respect to the entire mass of the liquid composition. In addition, regarding the mass ratio of the F particles to the inorganic particles in the liquid composition, when the mass of the F particles is set to 1, the mass of the inorganic particles is preferably 0.001 to 2.0. More specifically, in obtaining the aspect I In the case of this particle, the liquid composition preferably contains 20 to 50 mass % of F particles and 0.1 to 40 mass % of inorganic particles.

The liquid composition can be prepared by mixing F particles, inorganic particles, and a dispersion medium. Examples of mixing methods include the following methods: a method of adding F particles and inorganic particles to a dispersion medium at one time and mixing; a method of sequentially adding F particles and inorganic particles to the dispersion medium and mixing; pre-mixing F particles Particles and inorganic particles, the method of mixing the obtained mixture with the dispersion medium; the method of mixing the F particles and the dispersion medium, the inorganic particles and the dispersion medium in advance, and then mixing the obtained two mixtures. Specifically, after dispersing silica particles in a dispersion medium, this is added to a dispersion liquid containing F particles and mixed. This method facilitates the mixing of silica particles and F particles. If the mixed solution containing the F particles and the silica particles is destabilized and solidified, the F particles and the silica particles can be combined. In addition, as the dispersion medium, a compound or the like similar to the following liquid dispersion medium is suitably used.

The liquid composition containing the F particles can be stirred during the addition of the inorganic particles or after the addition. As an apparatus for stirring, the stirring apparatus provided with blades, such as a propeller blade, a turbine blade, a stirring blade, a shell-shaped blade, as a stirring blade, is mentioned, for example. In addition, the stirring speed at this time should just be a level which can disperse|distribute the inorganic substance particle efficiently in the liquid composition containing F particle, and it is not necessary to apply a high shear force to the F particle.

The stirring of the liquid composition includes, for example, stirring by the above-mentioned stirring device, or a Henschel mixer, a pressurized kneader, a Banbury mixer, or a planetary mixer; Mill, sand mill, sand grinder, Dyno mill (bead mill using grinding media such as glass beads or zirconia beads), Dispermat, SC mill, nail crusher, or stirrer Mixing by a disperser using a medium such as a grinder; using a micro-spray homogenizer, a high-pressure homogenizer such as Nanomizer, and an Ultimaizer, an ultrasonic homogenizer, a dissolver, a disperser, a high-speed rotor disperser, and a rotating revolution mixer. Mixing by disperser. The shear treatment is preferably carried out under high shear conditions. "High shear" means stirring at a speed of at least over 300 rpm while stirring. The shearing treatment may be started in the middle of adding the inorganic particles to the liquid composition containing the F powder, or may be performed after the addition is completed.

As a method of removing the dispersion medium after the shearing treatment and isolating the particles, heating, decompression, or filtration may be mentioned, and an appropriate combination of these and the like may be used. Specific examples of the method for isolating the particles include the following methods: (1) the dispersion medium is distilled off under atmospheric pressure or reduced pressure to concentrate, filtered and dried if necessary; (2) one side The particles are agglomerated while the temperature of the liquid composition is adjusted, or after agglomeration and crystallization by adding an electrolyte, a coagulant, a coagulation aid, etc., and then separating and drying by means of filtration or the like; (3) the The liquid composition is sprayed into a drying gas whose temperature is adjusted to a temperature at which the dispersion medium can volatilize, dried and recovered; (4) the liquid composition is centrifuged and then dried. Here, as a drying method, vacuum drying, high frequency drying, and hot air drying are mentioned. In each of the above-mentioned methods (1) to (4), the liquid composition can be diluted with a dispersion medium as necessary, and the total content of the F polymer and inorganic substances in the liquid composition can be adjusted in advance.

In order to further improve the adhesion (adhesion) between the F particles and the inorganic particles when the particles are produced by the above-mentioned dry method A, dry method B, and wet method, it is preferable to mix the F particles and the inorganic particles before mixing. , or surface treatment of F particles at the same time as mixing. The surface treatment includes plasma treatment, corona discharge treatment, corona discharge treatment, etching treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, and ozone exposure treatment, and plasma treatment, especially low-temperature plasma treatment, is preferred. In addition, according to the dry method A and the dry method B, when the F particles collide with the inorganic particles, heat is easily uniformly transferred to these particles, and the present particles are easily densified and spherical. In this case, the sphericity of the present particle is preferably 0.5 or more, preferably 0.93 to 0.99.

In the production of the present particles, the D50 of the F particles is preferably 20 μm or less, more preferably 10 μm or less. D50 of the F particles is preferably 0.01 μm or more, more preferably 0.1 μm or more. Moreover, it is preferable that D90 of F particle is 10 micrometers or less. At D50 and D90 within this range, the fluidity and dispersibility of the F particles become good, and the size of the particles present in the dispersion medium can be easily controlled by the wet method so as to prevent precipitation. The bulk density of the F particles is preferably 0.15 g/m ² or more, more preferably 0.20 g/m ² or more. The bulk density of the F particles is preferably 0.50 g/m ² or less, more preferably 0.35 g/m ² or less.

The particles of the present invention can be stably dispersed even if they are added to a liquid dispersion medium in large amounts. The physical properties (electrical properties, adhesiveness, etc.) based on the F polymer and the physical properties (low linear expansion, etc.) based on the inorganic material are highly expressed. In addition, the physical properties (UV absorptivity, etc.) based on the aromatic polymer are likely to be highly expressed.

In this dispersion liquid A, the liquid dispersion medium is preferably a compound that is liquid at atmospheric pressure and 25°C. The liquid dispersion medium may be polar or non-polar, preferably polar. The liquid dispersion medium is more preferably at least one selected from the group consisting of water, amides, ketones and esters. The boiling point of the liquid dispersion medium is preferably in the range of 50 to 240°C. A liquid dispersion medium may be used individually by 1 type, and may use 2 or more types together. When the above-mentioned liquid dispersion medium is used, it is considered that the dispersed state of the present particles in the present dispersion liquid A can be more stably maintained. Examples of the liquid dispersion medium include water, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, -Butoxy-N,N-dimethylpropionamide, N-methyl-2-pyrrolidone, γ-butyrolactone, cyclohexanone, cyclopentanone, butyl acetate, methyl isopropyl Ketone, methyl ethyl ketone, toluene, preferably water, N-methyl-2-pyrrolidone, γ-butyrolactone, methyl ethyl ketone, cyclohexanone and cyclopentanone, more preferably N - Methyl-2-pyrrolidone, methyl ethyl ketone. The content of the liquid dispersion medium in the dispersion liquid A is preferably 30 to 90% by mass, more preferably 50 to 80% by mass.

The present dispersion liquid A further contains an aromatic polymer. The content of the aromatic polymer in the dispersion liquid A is preferably 0.1% by mass or more, more preferably 1% by mass or more. 40 mass % or less is preferable, and, as for content of an aromatic polymer, 20 mass % or less is more preferable. Moreover, it is preferable that the content of the aromatic polymer in this dispersion liquid A is less than the content of the said particle|grains. Specifically, the mass ratio (mass ratio) of the content of the aromatic polymer in the present dispersion A to the content of the present particles is preferably 0.01 or more, more preferably 0.1 or more. On the other hand, the above-mentioned comparison is preferably 0.5 or less, more preferably 0.3 or less. Even when the aromatic polymer is contained in the above-mentioned ratio, the present dispersion liquid A is excellent in state stability due to the above-mentioned mechanism of action.

Aromatic polymers can be either thermoset or thermoplastic, preferably thermoplastic. In this case, the dispersion stability of this dispersion liquid A becomes excellent. Examples of the aromatic polymer include a unit having an amide bond, a unit having an amide bond, or an N-substituted maleimide structure, a succinimide structure, or a phthalimide structure. The aromatic polymers (specifically, aromatic polyimide, aromatic polyimide imide, aromatic polyimide imide precursor, aromatic maleimide, aromatic polyimide, etc.) Aromatic polyamides (aromatic polyamides, aromatic polyamides), polyphenylene ethers, liquid crystal polyesters, or aromatic elastomers (styrene elastomers, etc.) as precursors of imide.

The aromatic polyimide is more preferably a semi-aromatic polyimide having an aromatic ring in either tetracarboxylic dianhydride or diamine, or a wholly aromatic polyimide having both aromatic rings amine. Specific examples of the aromatic polyimide include "UPIA (registered trademark)-AT" series (manufactured by Ube Industries, Ltd.), "Neopulim" series (manufactured by Mitsubishi Gas Chemical Corporation), "SPIXAREA" series (SOMAR) company), "Q-PILON" series (manufactured by PI Technology Research Institute), "WINGO" series (manufactured by Wingo Technology Co., Ltd.), "TOHMIDE" series (manufactured by T&K TOKA Co., Ltd.), "KPI-MX" series (Kawamura Sangyo Co., Ltd. manufacture). As a specific example of an aromatic polyimide imide or its precursor, "HPC-1000" and "HPC-2100D" (both are manufactured by Showa Denko Materials Co., Ltd.) are mentioned.

As the aromatic maleimide, maleimide resins having an N-substituted maleimide structure are preferred, and examples include bismaleimide resins, which are dimerized diamines having It is obtained by reacting a diamine such as a diamine having an alicyclic structure with a reactant of a tetracarboxylic dianhydride having an aromatic ring, and a polyimide having an amine group as a terminal group and maleic anhydride. The bismaleimide resin may have an N-substituted maleimide structure only at the terminal group, or may have an N-substituted maleimide structure at both the terminal group and the side chain. These maleimide compounds can be commercially available from the BMI series manufactured by DESIGNER MOLECULES Inc.

As the liquid crystal polyester, aromatic polyester or aromatic polyester amide to which an amide bond is introduced into the aromatic polyester can be mentioned. An isocyanate-derived bond, such as an imide bond, a carbonate bond, a carbodiimide bond, or an isocyanurate bond, can be introduced into the aromatic polyester or the aromatic polyester imide. The liquid crystal polyester is preferably a thermoplastic, more preferably a liquid crystal polyester having a melting temperature in the range of 260 to 360°C, and more preferably in the range of 270 to 350°C. Among the liquid crystalline polyesters, it is preferable to include at least a unit based on p-hydroxybenzoic acid (HBA) or a polyester based on a unit based on 6-hydroxy-2-naphthoic acid (HNA), preferably: a unit containing HBA and HNA unit The polyester; the aromatic hydroxycarboxylic acid unit comprising at least one of HBA or HNA, the aromatic diol unit of at least one of 4,4'-dihydroxybiphenyl or hydroquinone, and terephthalic acid, m- Polyester of aromatic dicarboxylic acid unit of at least one of phthalic acid or 2,6-naphthalene dicarboxylic acid; polyester comprising HBA unit and 2,6-dihydroxynaphthoic acid unit; comprising 2,6-dihydroxynaphthalene Polyester of formic acid unit, terephthalic acid unit and acetaminophen unit; polyester comprising HBA unit, terephthalic acid unit and 4,4'-biphenol unit. These liquid crystal polyesters can be obtained through industrial manufacturing, and examples include: “Vectra” series manufactured by Celanese Japan, “XYDAR” series by JX Energy, “LAPEROS” series by Polyplastics, Ueno "UENO LCP" series of pharmaceutical companies, etc.

The styrene elastomer is preferably a styrene elastomer having properties of both rubber and plastic, and being plasticized by heating to exhibit flexibility, such as styrene and conjugated diene or (methyl) Acrylate copolymer (styrene-butadiene rubber; styrene core-shell copolymer; styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer styrene-butadiene-styrene block copolymer, hydrogenated products of styrene-butadiene-styrene block copolymers, and styrene-based block copolymers such as hydrogenated products of styrene-isoprene-styrene block copolymers, etc.), preferably It is a styrene elastomer that has properties of both rubber and plastic, and is plasticized by heating to show flexibility.

Preferably in the present invention, the aromatic polymer is selected from the group consisting of aromatic polyimide, aromatic polyimide, aromatic polyamide imide, polyphenylene ether, liquid crystal polyester, and aromatic maleimide At least one of the groups formed. In addition, in order to obtain a higher dispersion stabilization effect of the dispersion liquid A, the above-mentioned aromatic polymer is preferably a thermoplastic, among which, a thermoplastic aromatic polyimide or an aromatic polyimide imide is more preferred, and further more preferred. A thermoplastic aromatic polyimide is preferred. In this case, it is considered that thermoplastic aromatic polyimide or aromatic polyimide imide acts as a surfactant or a viscosity modifier in the present dispersion A, or acts as both of them. Therefore, the liquid physical properties (viscosity, thixotropic ratio, etc.) of the dispersion liquid A are balanced, and the handleability thereof is easily improved. Moreover, the adhesiveness and low linear expansion property of the molded object formed from this dispersion liquid A were further improved.

Furthermore, in this dispersion liquid A, at least a part of the said aromatic polymer can be dispersed in particle form. In this case, a particulate liquid crystal polyester is suitably used. In the case of using a particulate liquid crystal polyester, the average particle diameter (D50) is preferably in the range of 1 to 40 μm, more preferably 5 to 20 μm. When the average particle diameter (D50) is within this range, the dispersion stability in the present dispersion liquid A is likely to be further improved.

This dispersion liquid A may further contain a surfactant, or may not contain it. When the present dispersion liquid A contains a surfactant, the content thereof is preferably 1 to 15% by mass, and the surfactant is preferably nonionic. As the surfactant, a glycol-based surfactant, an acetylene-based surfactant, a silicone-based surfactant, and a fluorine-based surfactant are preferable. In addition, the so-called fluorine-based surfactant refers to a compound having a hydrophilic part and a hydrophobic part containing a fluorine-containing organic group. One type of surfactant may be used, or two types may be used. When two kinds of surfactants are used, the surfactants are preferably a silicone-based surfactant and a glycol-based surfactant. Specific examples of surfactants include "FTERGENT" series (manufactured by NEOS Corporation), "Surflon" series (manufactured by AGC Seimi Chemical Co., Ltd.), "MEGAFAC" series (manufactured by DIC Corporation), "Unidyne" series (manufactured by Daikin Corporation) manufactured by Industrial Corporation), "BYK-347", "BYK-349", "BYK-378", "BYK-3450", "BYK-3451", "BYK-3455", "BYK-3456" (BYK-Chemie Japan Corporation), "KF-6011", "KF-6043" (Shin-Etsu Chemical Co., Ltd.), "Tergitol" series (Dow Chemical Corporation, "Tergitol TMN-100X", etc.).

This dispersion liquid A is excellent in dispersion stability and handleability even if it does not necessarily contain a surfactant, especially a fluorine-based surfactant, by the above-mentioned mechanism of action. This dispersion liquid A preferably does not contain a fluorine-based surfactant. The low dielectric dissipation factor and the like of the molded article formed from the present dispersion liquid A containing no fluorine-based surfactant are likely to be further improved.

In order to improve the adhesiveness and low linear expansion of the molded article formed from the dispersion liquid A, the dispersion liquid A may further contain resin materials other than the F polymer and the above-mentioned aromatic polymer. The resin material may be thermosetting or thermoplastic, or modified, and may be dissolved in the dispersion liquid A or dispersed therein without being dissolved. Examples of the above-mentioned resin material include tetrafluoroethylene-based polymers other than F polymers, acrylic resins, phenol-based resins, polyolefin resins, modified polyphenylene ethers, vinyl ester resins, urea resins, and phthalic acid. Diallyl ester resin, melamine resin, melamine resin, melamine-urea co-condensation resin, polycarbonate, epoxy resin, etc. In order to improve the electrical properties of the molded article formed from the present dispersion A, the resin material is preferably a tetrafluoroethylene-based polymer other than the F polymer. Examples of tetrafluoroethylene-based polymers other than the F polymer include polytetrafluoroethylene (PTFE), and examples thereof include high molecular weight PTFE, low molecular weight PTFE, and modified PTFE having fibrillar properties. Furthermore, low molecular weight PTFE or modified PTFE also includes copolymers of TFE and a very small amount of comonomers (HFP, PAVE, FAE, etc.). When this dispersion liquid A contains a resin material, its content is preferably 40 mass % or less with respect to this whole dispersion liquid A.

The present dispersion liquid A may further contain a tetrafluoroethylene-based polymer in addition to the F polymer contained in the present particles. In this case, this dispersion liquid A is also excellent in dispersion stability. The above-mentioned tetrafluoroethylene-based polymer may be the same type of polymer as the above-mentioned F polymer constituting the present particle, or may be a different type of polymer. Among them, PTFE or F polymer is preferable, PFA or FEP is more preferable, and the above-mentioned polymer (1) or polymer (2) is still more preferable. The above-mentioned tetrafluoroethylene-based polymer is preferably in the form of particles, and is preferably dispersed in the present dispersion A. Moreover, the particle|grains of the said tetrafluoroethylene type polymer may contain only a tetrafluoroethylene type polymer, and may contain a tetrafluoroethylene type polymer and other components (the said resin material etc.).

The present dispersion liquid A may further contain inorganic particles in addition to the inorganic particles contained in the present particles. Examples of the inorganic particles include those similar to the above-mentioned inorganic particles that can constitute the present particle. One type of inorganic particles may be used, or two or more types may be mixed and used. When the present dispersion liquid A further contains inorganic particles, the content thereof is preferably in the range of 1 to 50 mass % with respect to the present dispersion liquid A as a whole, and more preferably 5 to 30 mass %. Moreover, the ratio by mass (mass ratio) of the content of the inorganic particles in the present dispersion A with respect to the content of the present particles is preferably 0.01-2, more preferably 0.1-1.

In addition to the above components, the dispersion liquid A may further contain a thixotropy imparting agent, a viscosity modifier, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weathering agent, a Antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, various fillers and other ingredients.

The present dispersion liquid A can be prepared by mixing and stirring other components such as the present particles, an aromatic polymer, a liquid dispersion medium, and optionally the above-mentioned surfactant. When stirring, the stirring apparatus mentioned in the said wet method, and the method similar to the method used for shearing treatment can be applied. The content of the particles in the dispersion A is preferably 20% by mass or more, more preferably 40 to 80% by mass, with respect to the entire mass of the dispersion A. In addition, the content of the F polymer is preferably 10% by mass or more with respect to the entire mass of the present dispersion A. In addition, it is preferable that the mass of the F particles in the present particle is compared with the inorganic substance, and when the mass of the F particle is set to 1, the mass of the inorganic substance is 0.01 to 2.0. In order to be able to appropriately form a molded product such as a layer from the dispersion liquid A, the dispersion liquid A preferably contains 20 to 40 mass % of F particles, 5 to 40 mass % of an inorganic substance, and 0.1 to 30 mass % of an aromatic polymer. thing.

The viscosity of this dispersion A at 25℃ is 1000～100000 mPa·s. The viscosity of the dispersion liquid A at 25°C is preferably 5000 mPa·s or more, more preferably 10000 mPa·s or more. The viscosity of the dispersion liquid A at 25°C is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, and still more preferably 20,000 mPa·s or less. In this case, this dispersion liquid A is excellent in coatability, and it becomes easy to form the molded object (polymer layer etc.) which has an arbitrary thickness. In addition, with regard to the present dispersion liquid A having a viscosity in this range, especially a high viscosity, in the formed product formed from the dispersion liquid A, the inorganic substances are not easily aggregated and are easily uniformly distributed, so that the F polymer and the inorganic substances are more likely to be expressed at a higher level. materiality.

The thixotropy ratio of the dispersion liquid A is preferably 1.0 or more. The thixotropy ratio of the dispersion liquid A is preferably 3.0 or less, more preferably 2.0 or less. In this case, the present dispersion liquid A is excellent in coatability and homogeneity, and it is easy to form a denser molded product (polymer layer, etc.). This dispersion liquid A is easy to adjust to the viscosity and thixotropy in the above-mentioned range, and is excellent in workability.

In the present dispersion liquid A, the precipitation ratio of the components is preferably 60% or more, preferably 70% or more, and more preferably 80% or more. Here, the component precipitation rate refers to a value calculated by putting this dispersion liquid A (18 mL) in a spiral tube (internal volume: 30 mL), and leaving it to stand at 25°C At the time of 14 days, the height of the whole dispersion liquid in the spiral tube after standing and the height of the precipitation layer (dispersion layer) were calculated according to the following formula. In addition, when a precipitation layer was not confirmed after standing still, and the state did not change, it was considered that the height of the whole dispersion liquid did not change, and the component precipitation rate was set to 100%. Component precipitation rate (%) = (height of the precipitation layer) / (height of the entire dispersion) × 100

This dispersion liquid A is brought into contact with the surface of the base material layer, and heated to form a polymer layer, thereby obtaining a laminate having a base material layer and a polymer layer. More specifically, when the dispersion liquid A is brought into contact with the surface of the base material layer to form a liquid coating, the liquid coating is heated to remove the dispersion medium to form a dry coating, and the dry coating is further heated. By calcining the F polymer, the following layered product can be obtained. The layered product has a polymer layer (hereinafter also referred to as "F layer") containing the F polymer and an inorganic substance on the surface of the base material layer, preferably containing F Polymer layer of polymer and silica. The temperature at the time of heating the liquid coating film is preferably 120°C to 200°C. On the other hand, the temperature at the time of heating to dry the film is preferably 250 to 400°C, more preferably 300 to 380°C. As each heating method, a method of using an oven, a method of using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays can be mentioned.

Examples of the base material layer include metal substrates such as metal foils such as copper, nickel, aluminum, titanium, and alloys thereof; polyimide, polyarylate, polyamide, polyarylene, polyamide, and polyether amide. Films of heat-resistant resins such as amine, polyphenylene sulfide, polyaryletherketone, polyamide imide, liquid crystal polyester, and liquid crystal polyester imide; prepreg (precursor of fiber-reinforced resin substrate), silicon carbide , aluminum nitride, silicon nitride and other ceramic substrates, glass substrates. The ten-point average roughness of the surface of the base material layer is preferably 0.01 to 0.05 μm. The contact of the dispersion liquid A is preferably performed by coating, droplet discharge, and immersion, and is preferably performed by coating. Examples of coating methods include spray coating, roll coating, spin coating, gravure coating, microgravure coating, gravure offset coating, blade coating, contact coating, and bar coating. method, die nozzle coating method, injection Meeller rod method, slot die nozzle coating method.

When drying the liquid coating, the liquid coating is heated at a temperature at which the dispersion medium is volatilized to form a dry coating on the surface of the sheet-like substrate. The heating temperature is preferably the boiling point of the dispersion medium +50°C or lower, more preferably the boiling point of the dispersion medium or lower, and still more preferably the boiling point of the dispersion medium -50°C or lower. The temperature during drying is preferably 120°C to 200°C. Furthermore, air may be blown in the step of removing the dispersion medium. When drying, the dispersion medium does not need to be completely volatilized, as long as it is volatilized to the extent that the shape of the layer is stable and the self-supporting film can be maintained. When the F polymer is calcined, the dry film is preferably heated at a temperature higher than the melting temperature of the F polymer. The heating temperature is preferably 380°C or lower, more preferably 350°C or lower. As each heating method, a method of using an oven, a method of using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays can be mentioned. Heating can be carried out under either normal pressure or reduced pressure. Moreover, the heating atmosphere may be any of an oxidizing gas atmosphere (oxygen, etc.), a reducing gas atmosphere (hydrogen, etc.), and an inert gas atmosphere (helium, neon, argon, nitrogen, etc.). The heating time is preferably 0.1 to 30 minutes, more preferably 0.5 to 20 minutes. If the heating is performed under the above conditions, the F layer can be appropriately formed while maintaining high productivity.

The thickness of the F layer is preferably 0.1-150 μm. Specifically, when the base material layer is a metal foil, the thickness of the F layer is preferably 1 to 30 μm. When the base material layer is a heat-resistant resin film, the thickness of the F layer is preferably 1 to 150 μm, more preferably 10 to 50 μm. The peel strength between the F layer and the base material layer is preferably 10 N/cm or more, more preferably 15 N/cm or more. The above-mentioned peel strength is preferably 100 N/cm or less. When the present dispersion liquid A is used, the above-mentioned present layered body can be easily formed without sacrificing the physical properties of the F polymer in the F layer.

The dispersion liquid A may be in contact with only one surface of the substrate layer, or may be in contact with both surfaces of the substrate layer. In the former case, a laminate having a base material layer and an F layer on one surface of the base material layer can be obtained, and in the latter case, a base material layer and an F layer on both surfaces of the base material layer can be obtained. layered body. The latter laminate is less likely to be warped, and thus is excellent in workability during processing. Specific examples of the above-mentioned laminate include a metal foil laminate having a metal foil and having an F layer on at least one surface of the metal foil, and a polyimide film having a polyimide film on both surfaces of the polyimide film. Multilayer film of layer F.

In addition, as a metal foil, the metal foil with a carrier which consists of two or more layers of metal foils can be used. Examples of the metal foil with a carrier include the following copper foil with a carrier, which includes a carrier copper foil with a thickness of 10 to 35 μm and an ultra-thin copper with a thickness of 2 to 5 μm laminated on the carrier copper foil through a peeling layer. foil. If the copper foil with the carrier is used, a fine pattern can be formed by the MSAP (modified semi-additive method) process. The peeling layer is preferably a metal layer containing nickel or chromium, or a multi-layer metal layer in which the metal layer is laminated. As a specific example of the metal foil with a carrier, the trade name "FUTF-5DAF-2" by Futian Metal Foil Powder Industry Co., Ltd. can be mentioned.

The outermost surface of the above-mentioned layered product may be further subjected to surface treatment in order to further improve the low linear expansion property or the adhesiveness. Here, the outermost surface of the laminate refers to the surface of the F layer on the side opposite to the base material. As a method of surface treatment, corona treatment, plasma treatment, ozone treatment, excimer treatment, and silane coupling treatment can be mentioned. As a gas used for plasma processing, rare gases, such as oxygen, nitrogen, and argon, hydrogen, ammonia, and vinyl acetate are mentioned. These gases may be used alone or in combination of two or more. In order to further improve the low linear expansion coefficient of the above-mentioned laminated body, annealing treatment may be further performed. The conditions in the annealing treatment are preferably 120 to 180° C. for temperature, 0.005 to 0.015 MPa for pressure, and 30 to 120 minutes for time.

Other substrates can be further laminated on the outermost surface of the laminated body. Examples of other substrates include a heat-resistant resin film, a prepreg as a precursor of a fiber-reinforced resin sheet, a laminate having a heat-resistant resin film layer, and a laminate having a prepreg layer. Furthermore, the prepreg system is a sheet-like substrate obtained by impregnating a thermosetting resin or a thermoplastic resin into a base material such as tow of reinforcing fibers such as glass fiber or carbon fiber, or a woven cloth. The heat-resistant resin film is a film containing one or more types of heat-resistant resins. Examples of the heat-resistant resin include the above-mentioned resins, and aromatic polyimide is particularly preferred.

As a lamination method, the method of heat-pressing a laminated body and another board|substrate is mentioned. When the other substrates are prepregs, the conditions of the hot pressing are preferably set to the temperature of 120 to 400°C, the pressure of the atmosphere to a vacuum of 20 kPa or less, and the pressing pressure to be 0.2 to 10 MPa. The above-mentioned laminate has an F layer excellent in electrical properties, and thus is suitable as a printed circuit board material. Specifically, the above-mentioned laminate can be used as a flexible metal foil laminate or a rigid metal foil laminate to produce a printed circuit board, and is particularly suitable for use as a flexible metal foil laminate to produce a flexible printed circuit board.

The metal foil of the laminated body such as the metal foil with the F layer in which the base material layer is a metal foil is etched, a transmission circuit is formed, and a printed circuit board is obtained. Specifically, the printed circuit board can be produced by the following methods: a method of etching a metal foil to process it into a specific transmission circuit; or by a semi-additive method (SAP method), an electroplating method such as MSAP method, etc. A method of processing into a specific transmission circuit. The printed circuit board made of the metal foil with the F layer has the transmission circuit formed of the metal foil and the F layer in this order. As a specific example of the structure of a printed circuit board, a transfer circuit/F layer/prepreg layer, a transfer circuit/F layer/prepreg layer/F layer/transfer circuit are mentioned. When manufacturing the printed circuit board, an interlayer insulating film may be formed on the transmission circuit, a solder resist may be laminated on the transmission circuit, and a cover film may be laminated on the transmission circuit. These interlayer insulating films, solder resists, and cover films can be formed using this dispersion liquid A.

The laminate of the F layer and other substrates can be used as antenna parts, printed circuit boards, aircraft parts, automotive parts, sports equipment, food industry supplies, coatings, cosmetics, etc. Specifically, it can be used as a wire covering material ( Aircraft wires, etc.), electrical insulating tapes, insulating tapes for oil drilling, materials for printed circuit boards, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), Electrode binders (for lithium secondary batteries, fuel cells, etc.), replica rolls, furniture, car dashboards, home appliances, etc. covers, sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belts) Conveyors, food conveying belts, etc.), tools (shovels, files, awls, saws, etc.), boilers, funnels, pipes, ovens, baking molds, chutes, eye molds, toilets, container coverings.

The second dispersion liquid of the present invention is the following dispersion liquid (hereinafter also referred to as "the present dispersion liquid B"), which comprises the present particles and a liquid dispersion medium, and the present particles are dispersed in the above-mentioned liquid dispersion medium, and the above-mentioned liquid dispersion medium The dispersion medium includes two liquid dispersion media having different boiling points, and the two liquid dispersion media are in a relationship of forming an azeotrope.

The dispersion stability of this dispersion liquid B was excellent. In addition, the molded article obtained from the present dispersion B is relatively dense, and has excellent surface properties such as appearance (surface flatness and texture). The reasons for the improvement of the dispersion stability of the dispersion liquid B and the appearance of the obtained molded product, and the correlation and action mechanism with the constitution of the dispersion liquid B are not necessarily clear, but are considered as follows. Composite particles containing tetrafluoroethylene-based polymers and inorganic substances are generally easy to adsorb or support a dispersion medium. Therefore, after the dispersion liquid containing the composite particles is applied to the surface of the substrate to form a liquid coating, it takes time for volatilization or evaporation when the dispersion medium is removed by heating or the like, which tends to reduce the production efficiency and accuracy of the molded product. On the other hand, when a molded article is produced from a dispersion liquid, even if the dispersion medium constituting the dispersion liquid is easily volatilized or evaporated, the composite particles are not sufficiently accumulated, and the surface smoothness of the obtained molded article is easily caused. reduce. This dispersion liquid B contains two kinds of liquid dispersion media which have different boiling points and are in a relationship of forming an azeotrope as a dispersion medium, so it is considered that the dispersion medium can be volatilized at an appropriate evaporation rate. In addition, since the high-boiling liquid dispersion medium gradually volatilizes or evaporates, the particles are densely packed, and the surface roughness due to the rapid generation of air bubbles can be suppressed, thereby improving the quality of the obtained molded product. Exterior.

Moreover, this particle contains F polymer and an inorganic particle. Although the surface energy of the F polymer is lower and the dispersion stability is lower, the original particles formed by the combination of the F polymer and the inorganic matter are more likely to interact with other original particles and the liquid dispersion medium than the F polymer, so it is considered that Excellent dispersion stability. As a result, it is considered that the present dispersion B can form a molded article having high physical properties of the F polymer and inorganic properties, high component uniformity, relatively dense, and excellent electrical properties and appearance.

The details of the polymer F and the particles in the dispersion B are the same as those described in the description of the dispersion A above.

In addition, in the present dispersion B, the F particles constituting the present particles may also contain aromatic polyester, polyimide imide, thermoplastic polyimide, polyphenylene ether, polyphenylene oxide ) and the like other than the F polymer, but preferably the F polymer as the main component. The content of the F polymer in the F particles is preferably 80% by mass or more, more preferably 100% by mass.

The present particles can be stably dispersed even when a large amount is added to the liquid dispersion medium, and in the molded article (polymer layer, film, etc.) formed from the present dispersion liquid B, the F polymer and the inorganic matter are more uniformly distributed, and it is easy to The physical properties of F polymers (electrical properties, adhesion, etc.) and the properties of inorganic substances (low linear expansion, etc.) are highly expressed.

The present dispersion B contains two liquid dispersion media having different boiling points. In addition, the above-mentioned two liquid dispersion media are in a relationship to form an azeotrope. Here, an "azeotrope" is a mixture in which the composition of the gas phase and the liquid phase are the same. The azeotrope may be either homogeneous or heterogeneous depending on the choice of the two liquid dispersion media. A uniform azeotropic mixture is preferable from the viewpoint of improving productivity and step-throughability in the process of obtaining a molded product from the present dispersion B.

In this dispersion liquid B, it is preferable that the mixing ratio of the high-boiling point dispersion medium in the above-mentioned two liquid dispersion media with different boiling points is greater than that of the high-boiling point dispersion medium in the azeotrope of the above-mentioned two liquid dispersion mediums. Composition ratio (mass ratio). The compositional ratio of the azeotrope may vary widely depending on the choice of the two liquid dispersion media. Specifically, when the liquid dispersion medium with a low boiling point is used as the dispersion medium S1, and the liquid dispersion medium with a high boiling point is used as the dispersion medium S2, the composition ratio of S1 to S2 in the dispersion liquid B is preferably ( mass ratio) than the composition ratio (mass ratio) of S1 to S2 in the azeotrope of S1 and S2. Further, the azeotrope of the azeotropic mixture is preferably lower than the boiling point of the high-boiling point dispersion medium among the above-mentioned two liquid dispersion media, more preferably, the azeotrope point is lower than the boiling point of either of the above-mentioned two liquid dispersion media. With such a mixing ratio and azeotrope, even a dispersion medium having a relatively high boiling point can be easily removed as an azeotrope at a lower low temperature during the drying process when a molded product is produced from the present dispersion B. Therefore, it is easy to achieve both the improvement of productivity and the improvement of the appearance of the molded product. In addition, it is considered that the remaining high-boiling liquid dispersion medium also acts as a lubricant in the process of removing the liquid dispersion medium, promoting the accumulation of the particles, and assisting in the formation of a uniform molded product with less surface roughness.

Both of the above two liquid dispersion media are preferably compounds that are liquid at atmospheric pressure and 25°C, and may be polar or non-polar. Both of the above-mentioned two liquid dispersion media preferably have a boiling point in the range of 50 to 240°C. Furthermore, at least one of the two liquid dispersion media is more preferably water, alcohol or amide. When the above-mentioned liquid dispersion medium is used, it is considered that the dispersed state of the present particles in the present dispersion liquid B can be maintained more stably.

Examples of the liquid dispersion medium include water [boiling point: 100°C (boiling point at atmospheric pressure, the same applies when there is no particular description below)], ethylene glycol (boiling point: 197°C), N,N-dimethylformamide Amine (boiling point: 153°C), N,N-dimethylacetamide (boiling point: 165°C), 3-methoxy-N,N-dimethylpropionamide (boiling point: 215°C), 3- Butoxy-N,N-dimethylpropionamide (boiling point: 252°C), N-methyl-2-pyrrolidone (boiling point: 204°C), γ-butyrolactone (boiling point: 204°C), Cyclohexanone (boiling point: 156°C), cyclopentanone (boiling point: 131°C), butyl acetate (boiling point: 126°C), methyl isobutyl ketone (boiling point: 118°C), methyl ethyl ketone (boiling point: 118°C) : 79.6°C), toluene (boiling point: 111°C). Among them, as a combination of two liquid dispersion media suitable for the present dispersion B, which are in the relationship of forming an azeotrope and have different boiling points, water and methyl ethyl ketone, water and cyclohexanone, ethylene di Alcohol and toluene, toluene and N,N-dimethylformamide. In addition, in this specification, the combination of toluene and N,N- dimethylformamide is regarded as an azeotropic mixture whose azeotropic point is 59.9-109.9 degreeC.

The present dispersion liquid B may further contain another liquid dispersion medium different from the above-mentioned two liquid dispersion mediums within the range which does not impair the effect of the present invention. Here, the other liquid dispersion medium may form an azeotrope with at least one of the above-mentioned two liquid dispersion media, or may form a three-component azeotrope together with the above-mentioned two liquid dispersion mediums relationship, but preferably a relationship that does not generate any azeotrope. In the present dispersion liquid B, the total content of the liquid dispersion medium is preferably 30 to 90% by mass, more preferably 50 to 80% by mass.

This dispersion liquid B may further contain a surfactant, and may not contain it. As a surfactant, the thing similar to the surfactant mentioned in the description of this dispersion liquid A mentioned above can be mentioned. This dispersion liquid B preferably does not contain a fluorine-based surfactant.

In order to improve the adhesiveness and low linear expansion of the molded article formed from the dispersion liquid B, the dispersion liquid B may further contain other resin materials in addition to the particles. In this case, this dispersion liquid B also becomes excellent in dispersion stability. When this dispersion liquid B contains another resin material, its content is preferably 40 mass % or less with respect to the whole of this dispersion liquid B. As other resin materials, tetrafluoroethylene-based polymers other than F polymers, F polymers, and aromatic polymers can be mentioned. Other resin materials can be the same as the F polymer in this particle. Examples of tetrafluoroethylene-based polymers other than the F polymer include polytetrafluoroethylene (PTFE), polymers containing TFE units and ethylene-based units, polymers containing TFE units and propylene-based units, and TFE-containing units Units and polymers based on fluoroalkylethylene units, polymers comprising TFE units and units based on chlorotrifluoroethylene. The F polymer may be the same type of polymer as the above-mentioned F polymer constituting the present particle, or may be a different type of polymer. Among them, PTFE or F polymer is preferable, PFA or FEP is more preferable, and the above-mentioned polymer (1) or polymer (2) is still more preferable. The above-mentioned F polymer is preferably in the form of particles, and is preferably dispersed in the present dispersion liquid B. Moreover, the particle|grains of the said F polymer may contain only the F polymer, and may contain the F polymer and other components (the said resin material etc.).

As an aromatic polymer, the thing similar to the aromatic polymer which can be contained in dispersion liquid A is mentioned, and its preferable range is also the same.

The present dispersion liquid B may further contain inorganic particles in addition to the inorganic particles contained in the present particles. As the inorganic particles, the same inorganic particles as the inorganic particles which can be further contained in the dispersion liquid A can be mentioned, and the preferred aspects thereof are also the same. In addition to the above-mentioned components, the present dispersion liquid B may further contain other components similar to the other components described in the description of the present dispersion liquid A above within a range that does not impair the effects of the present invention.

The present dispersion liquid B can be prepared in the same manner as the present dispersion liquid A. The preferable ranges of the content of the present particles in the present dispersion B, the content of the F polymer, and the mass ratio of the F particles in the present particles to the inorganic matter are the same as those in the present dispersion A. The content of the F polymer in the dispersion liquid B is preferably 40% by mass or more, more preferably 50% by mass or more. When this dispersion liquid B contains F polymer as other resin in addition to the F polymer contained in this particle, the content of F polymer in this dispersion B means the F polymer contained in this particle The sum of the content of F and the content of the F polymer contained as other resins.

The preferred ranges of viscosity, thixotropy ratio and component precipitation ratio of this dispersion B are the same as the preferred ranges of viscosity and thixotropy ratio of this dispersion A.

When this dispersion liquid B is brought into contact with the surface of the base material layer and heated to form a polymer layer containing the F polymer and an inorganic substance, a laminate having a base material layer and a polymer layer can be obtained. The details of the method for producing the laminate, the substrate layer, the aspect of the printed circuit board using the laminate, and the multilayer printed circuit board, including the preferred aspect, are the same as those described in the description of the above-mentioned dispersion A. same.

Furthermore, when drying the liquid coating film, the liquid coating film is heated at a temperature at which the dispersion medium is volatilized to form a dry coating film on the surface of the sheet-like base material. The temperature of the above heating is preferably below the azeotropic point +50°C of the azeotropic mixture of the two dispersion media contained in the dispersion B, more preferably below the azeotropic point. The temperature during drying is preferably 120°C to 200°C.

The composite particles of the present invention are composite particles (hereinafter also referred to as "the present particles α") containing F polymers having a melting temperature of 260 to 320° C. and 1 to 5 mol% of PAVE units relative to the total units , and silica, wherein the amount of silicon atoms in the surface of the composite particles measured by X-ray photoelectron spectroscopy is 1 or more relative to the amount of fluorine atoms.

The particle α is a composite material of F polymer and silicon dioxide, which can adjust the physical properties such as polarity, and has high stability. Although the mechanism of action is not clear, it is considered as follows. The F polymer not only has excellent shape stability such as fibrillation resistance, but also has a configuration with a high degree of freedom in which the restriction of molecular motion at the single-molecule level is relaxed. The above-mentioned F polymer is likely to form microscopic spherulites at the molecular aggregate level, and microscopic concavo-convex structures are likely to be formed on the surface thereof. Therefore, it is considered that the molecular assembly of the F polymer will stably and physically closely adhere to the silica without loss of its shape. In addition, it is also considered that the interaction between the closely adhered silicas promotes the adhesion of the silicas, thereby stabilizing the composite particles. As a result, it is considered that this particle α has high stability even if it contains a relatively large amount of silica, and has the physical properties of the F polymer and the physical properties of silica.

The F polymer in the present particle α is a TFE-based polymer having a melting temperature of 260 to 320° C. and containing 1 to 5 mol % of PAVE units with respect to the total unit. As the F polymer, the above-mentioned polymer (1) containing a TFE unit and a PAVE unit and having a polar functional group is more preferable. If the F polymer is the polymer (1), in the particle α, the polymer (1) and the silica are easily attached not only physically but also chemically, and the above-mentioned action mechanism is easily strengthened.

The present particle α may also contain other polymers than the F polymer. However, the ratio of the F polymer in the polymer contained in the particle α is preferably 80% by mass or more, more preferably 100% by mass. Examples of polymers other than the F polymer include heat-resistant resins such as aromatic polyesters, polyimide imide, thermoplastic polyimide, polyphenylene ether, and polyoxyxylene.

This particle α contains silica. One type of silica may be used, or two or more types may be used in combination. Moreover, inorganic substances other than silica may be contained. In the case of containing other inorganic substances other than silica, the total amount of silica and other inorganic substances is set to 100% by mass, and the content of silica is preferably 50% by mass or more, more preferably 75% by mass. The content of silicon dioxide is preferably 100 mass % or less, more preferably 90 mass % or less.

Silica is preferably surface-treated at least a portion of its surface. As a surface treatment agent used for this surface treatment, the same compound as the surface treatment agent used for the surface treatment of the said inorganic substance is mentioned, for example, a silane coupling agent is mentioned.

The specific surface area (BET method) of silica is preferably 1-20 m ² /g, more preferably 5-8 m ² /g. In this case, the interaction between the silica and the F polymer is easily strengthened. In addition, when the dispersion liquid containing the particles α is applied to the substrate to form the polymer layer, the silica and the F polymer are more uniformly distributed, and it is easy to balance the physical properties of the two.

Examples of silica include silica fillers (“Admafine (registered trademark)” series manufactured by Admatechs, etc.), spherical fused silica (“SFP (registered trademark)” series manufactured by DENKA Corporation, etc.), Hollow silica fillers ("E-SPHERES" series manufactured by Pacific Cement Corporation, "SiliNax" series manufactured by Nippon Steel Mining Corporation, "Ecco sphere" series manufactured by Emerson & Cuming Corporation, hydrophobicity manufactured by Japan Aerosil Corporation AEROSIL series "RX200" etc.). Moreover, as another inorganic substance other than silica, the inorganic substance which can comprise this particle mentioned above is mentioned.

The shape of silica is preferably granular, more preferably spherical, needle-like (fibrous) or plate (column). Specific shapes of silica include spherical, scale-like, lamellar, leaf-like, almond-like, columnar, cockscomb, equiaxed, leaf-like, mica-like, massive, flat, wedge-like shape, rosette shape, net shape, angular column shape, preferably spherical shape. If spherical silica is used, when the dispersion liquid containing the particle α is applied to the substrate to form the polymer layer, the silica and the F polymer are more uniformly distributed, and the function thereof is easily improved. The spherical silica is preferably substantially spherical. Roughly true spherical shape as described above.

測定模式：寬光譜測定 結合能之測定範圍：0～1100 eV 通過能量：93.8 eV 能階：0.8 eV 累計數：16個循環 中和槍：使用 檢測器與試樣表面之角度：45度 本發明中，藉由ESCA來測定本粒子α中存在於該深度之元素，對矽原子之量及氟原子之量進行定量。本粒子α中，將如此定量之矽之量除以氟之量所獲得之值為1以上。When the particle α is measured by X-ray photoelectron spectroscopy (hereinafter also referred to as ESCA), the amount of silicon atoms on the surface is 1 or more relative to the amount of fluorine atoms. ESCA is a method for quantifying the amount of elements present on the surface of particles, etc. It is possible to quantify each element such as carbon (C), oxygen (O), fluorine (F), and silicon (Si). In the present invention, the surface is a depth of 2 to 8 nm from the surface of the particle. During the measurement, the particles were fixed with a carbon tape, and the particles were sampled while the carbon tape was not exposed and the surface flatness was ensured as much as possible. Device information and analysis conditions are described below. Analysis device: ESCA 5500 manufactured by ULVAC-PHI X-ray source: Al Kα 14 kV Beam diameter: 800 μm

Measurement mode: Broad spectrum measurement Binding energy measurement range: 0～1100 eV Pass energy: 93.8 eV Energy level: 0.8 eV Cumulative number: 16 cycles Neutralization gun: Use the angle between the detector and the surface of the sample: 45 degrees Among them, the elements present at the depth in the particle α were measured by ESCA, and the amount of silicon atoms and the amount of fluorine atoms were quantified. In this particle α, the value obtained by dividing the amount of silicon thus quantified by the amount of fluorine is 1 or more.

The present particle α having the above-mentioned value, in other words, the surface of which is highly coated with silica, is not only due to excellent particle properties such as dispersibility in a liquid of silica, but also a molded product formed from a liquid composition containing the present particle α. It is easy to have high physical properties of silica and physical properties of F polymer. The amount of silicon atoms in the surface of the present particle α obtained by ESCA measurement is preferably 1.0 or more, more preferably 1.1 or more, and still more preferably 1.2 or more with respect to the amount of fluorine atoms. The amount of silicon atoms is preferably 100 or less with respect to the amount of fluorine atoms.

Furthermore, the target elements in the ESCA measurement are set to four elements, namely carbon element, oxygen element, fluorine element, and silicon element, and the ratio (unit: Atomic%) of fluorine element and silicon element in the total is set to each atom. amount. In order to keep the amounts of fluorine atoms and silicon atoms on the surface of the particle α within the above-mentioned range, the particle α is preferably produced by the above-mentioned dry method A, dry method B, wet method, etc., more preferably dry method A . That is, it is preferable to make this particle|grain (alpha) by making F particle and silica collide at the temperature higher than the melting temperature of F polymer and in a suspended state.

D50 of the particle α is preferably 40 μm or less, more preferably 10 μm or less, and still more preferably 4 μm or less. D50 of the particle α is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 2 μm or more. In addition, D90 of the particle α is preferably 40 μm or less, more preferably 4 μm or less. When D50 and D90 of the present particle α are within the above-mentioned ranges, the dispersion stability of the present particle α, and when the polymer layer (layer F) is formed by applying the liquid composition containing the present particle α to the substrate, are in The dispersion uniformity in the polymer layer (F layer) etc. of the obtained layered product is further improved, and it becomes easy to obtain a layered product having high physical properties of the F polymer and physical properties of silica.

The larger the amount of silica in the particle α, the smaller the bulk density of the particle α, which is preferable. On the other hand, as the amount of silica in the particle α is smaller, the viscosity of the liquid composition containing the particle α becomes smaller, which is preferable. From the above viewpoints, the amount of silica in the particles α is preferably 15 to 85 parts by mass relative to 100 parts by mass of the F polymer. Within this range, the amounts of the fluorine element and the silicon element on the surface of the particle α can be easily adjusted within the above-mentioned range. The amount of silica in the particle α is more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, relative to 100 parts by mass of the F polymer. Moreover, as for the quantity of the silica in this particle|grain (alpha), 70 mass parts or less is more preferable with respect to 100 mass parts of F polymers, and 50 mass parts or less is still more preferable. By further setting it as the said range, it becomes easy to make the quantity of the fluorine atom and the silicon atom on the surface of this particle|grain (alpha) into the said range.

As a preferable aspect of the particle α, it is preferable that the F polymer is used as the core, and silica is attached to the surface of the core, that is, the aspect I described above.

In the case of Aspect I, the F polymer core and the silica are preferably in the form of particles, respectively. In this case, since silica with higher hardness than the F polymer is exposed on the surface, the fluidity of the particle α becomes high, and the handleability thereof is easily improved. Furthermore, in the case of Aspect I, the F polymer core may comprise a single F particle or an aggregate of F particles. In the present particle α of the aspect I, it is preferable to produce the F particles and the silica particles by the above-mentioned dry method A or dry method B, and the dry method A is more preferable. In this case, it is preferable to set the D50 of the F particles to be larger than the D50 of the silica particles, and to set the amount of the F particles to be larger than the amount of the silica particles. If this relationship is set, the present particle α of the aspect I can be easily obtained by producing the present particle α by the dry method A or the dry method B.

Based on the D50 of the F particles, the D50 of the silica particles is preferably 0.001-0.5, more preferably 0.01-0.05. Specifically, it is preferable that the D50 of the F particles exceeds 1 μm and the D50 of the silica particles is 0.8 μm or less. Regarding the present particle α of Aspect I thus obtained, the above relationship is maintained, the D50 of the F polymer core is greater than the D50 of the silica particle, and the mass occupied by the F polymer is greater than the mass occupied by the silica. In this case, the surface of the F polymer core is coated with a larger amount of silica particles, so that the present particle α of aspect I has a core-shell structure. Moreover, in this case, the aggregation of F particles is suppressed, and it is easy to obtain the original particle α in which silica particles are attached to the core including a single F particle.

In Aspect I, the silica particles are preferably spherical, more preferably substantially true spherical. The approximately true spherical shape is as follows. If the substantially spherical silica particles of this level are used, when the liquid composition containing the particle α is applied to the substrate to form a polymer layer, the silica and the F polymer are more uniformly distributed, and it is easy to Balance the physical properties of the two.

In aspect I, the D50 of the silica particles is preferably in the range of 0.001-0.8 μm, more preferably 0.01-0.3 μm, and still more preferably 0.03-0.1 μm. Silica having D50 in this range is also sometimes referred to as nano-silica. The handleability and fluidity of the particle α are easily improved, and the dispersion stability is easily improved. When the silica in this range is used, the liquid physical properties such as the viscosity and the thixotropic ratio of the liquid composition containing the particles α can be easily adjusted, and the handleability and defoaming properties thereof are excellent. In addition, the particle size distribution of the silica particles takes the value of D90/D10 as an index, and is preferably 3 or less, more preferably 2.9 or less. When the particle size distribution is narrow, it is easy to control the fluidity of the obtained particle α, which is preferable from the viewpoint.

In Aspect I, at least a part of the surface of the silica particles is preferably surface-treated, and more preferably, the surface is treated with a silazane compound such as hexamethyldisilazane, a silane coupling agent, or the like. . As a silane coupling agent, the above-mentioned compound is mentioned.

In Aspect I, one type of silica particles may be used, or two or more types may be mixed and used. When two kinds of silica particles are mixed and used, the average particle size of each silica particle may be different from each other, and the mass ratio of the content of each silica particle may be appropriately set according to the required function.

Also, in the case of Aspect I, it is preferred that a portion of the silica particles is embedded in the F polymer core. Thereby, the adhesiveness of the silica particles to the F polymer core is further improved, and it is more difficult for the silica particles to fall off from the particles α. That is, the stability of the present particle α is further improved. Regarding the particle α of the aspect I, the D50 of the F polymer core is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 2 μm or more. D50 is preferably 30 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less.

In addition, the ratio of the F polymer in the present particle α of Aspect I is preferably 50% by mass or more, more preferably 60% by mass or more. The ratio of the F polymer is preferably 99 mass % or less, more preferably 90 mass % or less, and still more preferably 80 mass % or less. The ratio of silica is preferably 1 mass % or more, more preferably 10 mass % or more, and still more preferably 20 mass % or more. 50 mass % or less is preferable, and 40 mass % or less is more preferable. In addition, when silica within this range is used, not only the present particles α excellent in handleability and dispersion stability can be easily obtained, but also the liquid physical properties such as the viscosity and thixotropic ratio of the liquid composition containing the present particles α can be easily adjusted. , so that its handleability and defoaming properties become excellent.

The present particle α of Aspect I may be further surface-treated. The specific example of this surface treatment is as described above, and it is possible to adjust not only the amount of silica on the surface of the particle α described above, but also the physical properties of the surface.

In the present invention, if the present particle α and the dispersion medium are mixed, a liquid composition (hereinafter also referred to as the present composition) can be obtained containing the present particle α and the dispersion medium, and the present particle α is dispersed in the dispersion medium. thing). This particle α can exhibit a sufficiently high polarity, and even if it is added in a large amount to a dispersion medium, it can be stably dispersed. In addition, in the polymer layer, laminate, and film formed from the present composition, the F polymer and the silica are more uniformly distributed, and the physical properties based on the F polymer, such as electrical properties, adhesiveness, etc., are easily exhibited at a high level, and Physical properties based on silica such as low linear expansion. The liquid dispersion medium in the present composition is a liquid compound that is inert at 25°C and functions as a dispersion medium for the particles α. The dispersion medium may be water or a non-aqueous dispersion medium. One type of dispersion medium may be used, or two or more types may be used. In this case, the different classes of liquid compounds are preferably compatible. As a dispersion medium, the same thing as the liquid dispersion medium in this composition A or this composition B is mentioned.

When the dispersion medium contains an aprotic polar solvent such as N-methyl-2-pyrrolidone, it is preferable that at least a part of the surface of the silica contained in the particle α is subjected to the following silane coupling agent. For the surface treatment, the silane coupling agent has at least one group selected from the group consisting of an amino group, a vinyl group, and a (meth)acryloyloxy group, and more preferably, the surface treatment is performed with a phenylaminosilane. When the dispersion medium contains a non-polar solvent such as toluene, it is preferable to hydrophobize at least a part of the surface of the silica contained in the particle α, preferably using a compound having a compound selected from an alkyl group and a phenyl group. The silane coupling agent of at least one group in the group is surface-treated. Furthermore, when the dispersion medium contains a protic polar solvent such as water, the silica contained in the particle α is preferably not surface-treated. When the above-mentioned dispersion medium is combined with the surface treatment of silica, the dispersion stability of the present composition becomes excellent.

When the composition is 100% by mass, the content of the particles α in the composition is preferably 1 to 50% by mass, more preferably 10 to 40% by mass. The content of the dispersion medium in the composition is preferably 50 to 99% by mass, more preferably 60 to 90% by mass, when the composition is 100% by mass.

In order to further improve the dispersion stability of the particles α and improve the particle precipitation and handleability, the composition may further contain a surfactant, but the particles α are excellent in dispersion stability, and therefore can be substantially free of surfactants. As a surfactant, the above-mentioned surfactant is mentioned. The so-called "substantially free of surfactant" means that the concentration of the surfactant in the composition does not exceed 1% by mass, the amount of the surfactant in the composition is less than 1% by mass, and the amount of the surfactant is preferably It is 0.5 mass % or less, More preferably, it is 0 mass %.

The viscosity of the composition is preferably 50 mPa·s or more, more preferably 100 mPa·s or more. The viscosity of the composition is preferably 50,000 mPa·s or less, preferably 1,000 mPa·s or less, and more preferably 800 mPa·s or less. In this case, since the present composition is excellent in coatability, it is easy to form a molded product such as a polymer layer having an arbitrary thickness. The thixotropy ratio of the present composition is preferably 1.0 or more. The thixotropy ratio of the present composition is preferably 3.0 or less, more preferably 2.0 or less. In this case, since the present composition is excellent not only in coatability, but also in homogeneity, it is easy to form molded articles such as a denser polymer layer.

The present composition may further comprise F polymers, polymers other than F polymers, or precursors thereof. Examples of the polymer or its precursor include polytetrafluoroethylene (PTFE), a polymer (PFA) containing a TFE unit and a PAVE unit, a polymer (FEP) containing a TFE unit and a hexafluoropropylene-based unit, Polymers containing TFE units and ethylene-based units (ETFE), polyvinylidene fluoride (PVDF), polyimide, polyarylate, polyarylene, polyarylene, polyamide, polyetheramide, polyamide Phenyl ether, polyphenylene sulfide, polyaryl ether ketone, polyamide imide, liquid crystal polyester, liquid crystal polyester imide, epoxy resin, maleimide resin, etc. Furthermore, the PFA may be an F polymer, or may be a PFA other than the F polymer. These polymers or their precursors can be dispersed or dissolved in the composition. Furthermore, these polymers or their precursors may be thermoplastic or thermosetting. The present composition preferably contains the above-mentioned aromatic polymer. In addition to the above-mentioned components, the present composition may further contain other components similar to the other components described in the description of the present dispersion liquid A within a range that does not impair the effects of the present invention.

As long as this composition is brought into contact with the surface of the base material layer and heated to form a polymer layer containing the F polymer and silica, a laminate having a base material layer and a polymer layer can be obtained. The details of the method for producing the laminate, the substrate layer, the aspect of the printed circuit board using the laminate, and the multilayer printed circuit board, including the preferred aspect, are the same as those described in the description of the above-mentioned dispersion A. same.

In addition, a film can be produced by melt-kneading the particles α and the fluoroolefin-based polymer and then extrusion-molding. The particle α contains the F polymer and silica having high interaction (compatibility) with the fluoroolefin-based polymer. In addition, the present particle α has silicon atoms in a specific ratio on the surface, so it has a specific hardness. When the present particle α and the fluoroolefin-based polymer are melt-kneaded, the composite particles collide with the fluoroolefin-based polymer and are pulverized respectively. Thus, it is easy to micronize. As a result, both are melt-kneaded uniformly, and in the obtained film, the F polymer, the fluoroolefin-based polymer, and the silica are uniformly distributed, and the F polymer and the fluoroolefin-based polymer are likely to be highly expressed. physical properties, especially electrical properties, and low linear expansion properties based on silica. The fluoroolefin-based polymer to be melt-kneaded with the particles α may be either the F polymer or a polymer containing a fluoroolefin-based unit other than the F polymer.

As a fluoroolefin type polymer, PTFE, PFA, FEP, ETFE, PVDF are mentioned. The PFA may be an F polymer or a PFA other than the F polymer. The fluoroolefin-based polymer may be the same F polymer as the F polymer contained in the composite particles. The melting temperature (melting point) of the fluoroolefin-based polymer is preferably 160 to 330°C. The glass transition point of the fluoroolefin-based polymer is preferably 45 to 150°C. The fluoroolefin-based polymer also preferably has a polar functional group. In addition, regarding the kind and introduction method of polar functional group, it is the same as that in the above-mentioned F polymer, including preferable type and introduction method.

The melt-kneading of the particles α and the fluoroolefin-based polymer can be performed, for example, using a uniaxial kneader. The single-shaft kneader has a material cylinder and a screw rotatably arranged in the material cylinder. When a uniaxial kneader is used, the deterioration of the F polymer and the fluoroolefin-based polymer can be easily prevented during melt-kneading. In this case, when the overall length of the screw is L (mm) and the diameter is D (mm), the effective length (L/D) expressed as the ratio of the overall length L to the diameter D is preferably 30 to 45. When the effective length is in the above range, the deterioration of the F polymer and the TFE-based polymer can be prevented, sufficient shear stress can be imparted to them, and the temperature unevenness of the melt-kneaded product can be easily reduced. The rotational speed of the screw is preferably 10-50 ppm.

The melt-kneaded material is ejected from the T-die head arranged at the front end of the material cylinder. Then, the melt-kneaded product ejected from the T-die is brought into contact with a plurality of cooling rolls to be solidified and formed into a film. The obtained long film is wound up to a take-up roll. The thickness of the film is preferably 5 to 150 μm, more preferably 10 to 100 μm. The shape of the film can be a long strip or a single sheet. The length in the longitudinal direction of the elongated film is preferably 100 m or more. The upper limit of the length in the longitudinal direction is usually 2000 m. In addition, the length in the short-side direction of the elongated shape is preferably 1000 mm or more. The upper limit of the length in the short side direction is usually 3000 mm.

After superimposing the obtained film on the base material layer, hot pressing is performed, whereby a laminate having a polymer layer formed of the film and a base material layer can be obtained. The conditions of the hot pressing are preferably set to the temperature of 120 to 300° C., the pressure of the atmosphere to be a vacuum of 20 kPa or less, and the pressurized pressure to be set to 0.2 to 10 MPa. In addition, about the aspect of a base material layer, the printed circuit board using a laminated body, and a multilayer printed circuit board, including preferable aspect, it is the same as the above-mentioned method 1 and the like. Also, a circular die may be used instead of a T-die to manufacture an blown film.

As mentioned above, although the dispersion liquid of this invention, composite particle, and the manufacturing method of a composite particle were demonstrated, this invention is not limited to the structure of the said embodiment. For example, the dispersion liquid and the composite particle of the present invention may be respectively added with other arbitrary structures to the structures of the above-described embodiments, or may be replaced with arbitrary structures that exhibit the same function. In addition, the method for producing composite particles of the present invention may have other optional steps in addition to the configuration of the above-described embodiments, or may be substituted for any steps that produce the same effect. Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these. The details of each component are shown below. [F particle] F particle 1: particle containing F polymer 1 (melting temperature 300°C) containing 97.9 mol % of TFE unit, 0.1 mol % of NAH unit, and 2.0 mol % of PPVE unit and having an acid anhydride group (D50: 2 μm; bulk density: 0.18 g/m ² ) F particle 2: F polymer 2 containing 97.5 mol % of TFE units and 2.5 mol % of PPVE units and having no functional group (melting temperature 305 °C) particles (D50: 2 μm; bulk density: 0.19 g/m ² ) F particles 3: particles containing F polymer 3 (melting temperature 305 °C) composed of only TFE units and PPVE units (D50: 2 μm; bulk density: 0.19 g/m ² ) F particles 4: F polymer 4 containing 97.5 mol % of TFE units and 2.5 mol % of PPVE units and having no polar functional group (melting temperature: 300° C.) PTFE particles (D50: 2.6 μm) [PTFE particles] PTFE1: particles containing non-thermofusible PTFE (D50: 0.3 μm; bulk density: 0.2 g/m ² ) PTFE2: particles containing fibrillar PTFE (D50 : 2.4 μm) [Inorganic substance] Inorganic substance 1: Silica filler (approximately true spherical shape, average particle size 0.03 μm), surface-treated with a silane coupling agent [Silicon dioxide particle] Silica particle 1: Contains dioxide Roughly spherical particles of silicon (D50: 0.05 μm) Silica particles 2: Roughly spherical particles containing silica (D50: 0.25 μm) [Dispersion medium] NMP: N-methyl-2-pyrrolidine Ketone Dispersion Medium S1: Toluene (Boiling Point: 111°C) Dispersion Medium S2: N,N-Dimethylformamide (DMF) (Boiling Point: 153°C) [Aromatic Polymer] Polymer 1: Thermoplastic Aromatic Polymer Varnish polymer 2 prepared by dissolving imide (PI1) in NMP: 2-hydroxy-6-naphthoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid, and 2,6-naphthalene diphenyl A thermoplastic polymer was obtained by reacting formic acid at a ratio of 60 mol %, 20 mol %, 15.5 mol %, and 4.5 mol % in this order, and the thermoplastic polymer was pulverized to obtain a powder (D50: 16 μm) . Polymer 3: Powder of thermosetting aromatic bismaleimide (D50: 2 μm)

[Example 1-1] 1. Manufacture of composite particles A mixture of 99 parts by mass of the F particles 1 and 1 part by mass of the inorganic substance 1 was prepared. Then, put the mixture into the following powder processing device (Hybridization System), the powder processing device is in a cylindrical container while stirring the particles with a high-speed rotating stirring blade, and on the other hand between the inner wall of the container and the stirring body. Stress is applied by clamping the particles. Then, the F particles 1 and the inorganic substances 1 are suspended and collided in a high-temperature turbulent atmosphere, and a stress is applied between them to perform a composite treatment. In addition, the inside of the apparatus during processing was made into nitrogen atmosphere, the temperature was kept below 100 degreeC, and the processing time was made into 15 minutes. The obtained treated product was in the form of fine powder. Further, the fine powder was analyzed with an optical microscope, and as a result, it was a composite particle 1 of a core-shell structure in which the F particle 1 was used as a core and the inorganic substance 1 was adhered to the surface of the core to form a shell. In addition, the shape of the composite particle 1 was spherical, and its D50 was 4 μm.

2. Manufacture and evaluation of dispersion liquid The NMP and the polymer 1 were added to the tank equipped with a stirring blade, and the tank was fully stirred. Then, the obtained composite particles 1 were put into the tank, stirred at 800 rpm for 15 minutes, and sheared in a state where an upflow was formed to obtain composite particles 1 (100 parts by mass) and polymer 1 (30 parts by mass). parts) and dispersion 1 of NMP (120 parts by mass). The viscosity of the obtained dispersion liquid 1 at 25°C was 18000 mPa·s. The dispersion stability and component precipitation rate of Dispersion Liquid 1 were evaluated according to the following criteria. <Evaluation Criteria for Dispersion Stability> ○: There was little foaming immediately after preparation and storage, and no aggregates were found, and the mixture was uniformly dispersed. Δ: A part of the aggregate was observed immediately after preparation and after storage. ×: A large amount of aggregates were found and were not uniformly dispersed. <Evaluation Criteria for Component Precipitation Rate> ○: The component precipitation rate is 60% or more. Δ: The component precipitation ratio exceeds 40% and is 60% or less. ×: The component precipitation ratio is 40% or less.

3. Fabrication and evaluation of laminates On the surface of a long copper foil (thickness 18 micrometers), the dispersion liquid 1 was apply|coated using a bar coater, and a wet film was formed. Next, the copper foil on which the wet film was formed was passed into a drying furnace at 110° C. for 5 minutes, and dried by heating to form a dry film. The dry film was then heated at 380°C for 3 minutes in a nitrogen oven. Thereby, the laminated body 1 which has the polymer layer (thickness 20 micrometers) which is a molded object of copper foil and the melt-fired product containing the F particle 1, the inorganic substance 1, and the polymer 1 located on the surface was produced. Cut out a square test piece of 180 mm square from the laminated body 1, and measure the linear expansion coefficient of the test piece in the range of 25°C to 260°C according to the measurement method specified in JIS C 6471:1995, and according to the following evaluated against the above-mentioned benchmarks. <Evaluation Criteria for Coefficient of Linear Expansion> ○: The linear expansion coefficient is 50 ppm/°C or less. Δ: The linear expansion coefficient exceeds 50 ppm/°C and is 75 ppm/°C or less. ×: The linear expansion coefficient exceeds 75 ppm/°C.

[Example 1-2] A mixture of 99 parts by mass of the F particles 1 and 1 part by mass of the inorganic substance 1 was prepared. Then, the mixture is put into the following powder processing apparatus (mechanical fusion apparatus), which is provided with a cylindrical rotating body having a receiving surface on its inner peripheral surface, and an internal member provided with a slight distance from the receiving surface. . Then, the cylindrical rotating body is rotated at a high speed around the central axis. The particles are pressed against the receiving surface by the centrifugal force generated at this time, and the mixture is introduced into the narrow space (pressing space) between the receiving surface and the internal member, and the particles are collided in a sheared state and processed. In addition, the temperature of the atmosphere of the cylindrical rotating body being processed was kept below 100 degreeC, and the processing time was made into 15 minutes. The obtained treated product was in the form of fine powder. The fine powder was analyzed with an optical microscope. As a result, it was a composite particle 2 of a core-shell structure in which the F particle 1 was used as a core and the inorganic substance 1 was adhered to the surface of the core to form a shell. In addition, the shape of the composite particle 2 was spherical, and its D50 was 18 μm. Using the obtained composite particles 2, a dispersion liquid 2 was produced in the same manner as in Example 1-1, and a layered body 2 was produced and evaluated. The evaluation results are shown in Table 1.

[Example 1-3 to Example 1-8] The composite particles 3 and 4 and the dispersion liquids 3 to 8 were obtained in the same manner as in Example 1-1, except that the types and amounts of the components were changed as shown in Table 1 below, and the laminated bodies 3 to 8 were produced. Table 1 shows the evaluation results of the obtained dispersion liquid and layered product.

[Table 1] Table 1 example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 Dispersion No. 1 2 3 4 5 6 7 8 Composition of the dispersion Composite particles (F particles) F particle 1 (mass part) 99 99 99 99 99 F particle 2 (mass part) 99 PTFE1 (parts by mass) 99 Composite particles (inorganic) Inorganic substance 1 (mass part) 1 1 1 1 1 1 1 (composite particle number) 1 2 3 1 1 1 4 Aromatic polymers Polymer 1 (parts by mass) 30 30 30 90 30 30 Polymer 2 (parts by mass) 30 Polymer 3 (parts by mass) 30 F particles F particle 1 (mass part) 200 99 Inorganic Inorganic substance 1 (mass part) 1 dispersion medium NMP (parts by mass) 120 120 120 120 120 360 120 120 Dispersion evaluation Dispersion stability 〇 〇 △ 〇 △ 〇 × × Component Precipitation Rate 〇 〇 △ 〇 △ 〇 × △ Viscosity(25℃)(mPa・s) 18000 19000 21000 19000 22000 20000 80000 60000 Laminated body evaluation Linear expansion coefficient 〇 〇 △ 〇 △ 〇 × ×

[Example 2-1] 1. Manufacture of composite particles A mixture of 99 parts by mass of F particles 1 and 1 part by mass of inorganic substance 1 was prepared, and composite particles 1 were obtained in the same manner as in 1. of Example 1-1. In addition, the shape of the composite particle 1 was spherical, and its D50 was 4 μm.

2. Manufacture and evaluation of dispersion liquid The dispersion medium S1 (toluene), the dispersion medium S2 (DMF), and the composite particle 1 obtained above were added to a tank equipped with a stirring blade, and the mixture was stirred at 800 rpm for 15 minutes to obtain a composite particle 1 (100 parts by mass), toluene ( 30 parts by mass) and dispersion 9 of DMF (70 parts by mass). The viscosity of the obtained dispersion liquid 9 at 25°C was 13000 mPa·s. The dispersion stability of the dispersion liquid 9 was evaluated in the same manner as in 2. of Example 1-1.

3. Production and evaluation of dry films and laminates On the surface of the long copper foil (thickness 18 μm), the dispersion liquid 9 was applied using a bar coater to form a wet film. Next, the metal foil on which the wet film was formed was passed into a drying furnace at 100° C. for 5 minutes, and dried by heating to obtain a dry film 1 . The smoothness of the dry film 1 was evaluated by visual observation and according to the following criteria. ＜Smoothness of dry film＞ 〇: The entire surface is smooth. Δ: Aggregates or irregularities due to powder falling off were observed at the edge of the surface. ×: Aggregates or irregularities due to powder falling off were observed on the entire surface.

Furthermore, the metal foil with the dry film 1 was heated in a nitrogen oven at 380° C. for 3 minutes to produce a metal foil and a molten calcined product including the F particles 1 on the surface, the inorganic substance 1 and the polymer. Laminate 1 of polymer layer 1 (thickness 20 μm). In the polymer layer, no aggregates or irregularities due to foaming were found, and the polymer layer was excellent in surface smoothness.

[Example 2-2 to Example 2-5] The composite particles 5 and the dispersions 10 to 13 were obtained in the same manner as in Example 2-1, except that the types and amounts of the components were changed as shown in Table 2 below, and the dry films 2 to 5 were produced. Table 2 shows the evaluation results of the obtained dispersion liquid and dry film.

[Table 2] Table 2 example 2-1 2-2 2-3 2-4 2-5 Dispersion No. 9 10 11 12 13 Composition of the dispersion Composite particles (F particles) F particle 1 (mass part) 99 99 F particle 3 (mass part) 99 99 99 Composite particles (inorganic) Inorganic substance 1 (mass part) 1 1 1 1 1 (composite particle number) 1 5 1 5 5 F particles F particle 1 (mass part) 100 Dispersion medium S1 Toluene (parts by mass) 30 30 60 100 Dispersion medium S2 DMF (parts by mass) 70 70 140 100 Dispersion evaluation Dispersion stability 〇 △ 〇 △ × Viscosity(25℃)(mPa・s) 13000 15000 13000 18000 25000 Dry film evaluation Smoothness of dry film 〇 △ 〇 × ×

[Example 3-1] 1. Production of composite particles A mixture of 70 parts by mass of F particles 1 and 30 parts by mass of silica particles 1 was prepared. Then, the mixture was put into the following powder processing device (Hybridization System (registered trademark)), which was in a cylindrical container while stirring the particles with a stirring blade rotating at a high speed, and on the inner wall of the container while stirring the particles. Stress is applied by sandwiching the particles between the stirring blades. Then, the F particles 1 and the silicon dioxide particles 1 are suspended and collided in a high-temperature turbulent atmosphere, and stress is applied between them to perform a composite treatment. In addition, the inside of the apparatus in process was set to nitrogen atmosphere, the temperature was maintained at 120 degrees C or less, and the composite treatment time was set to 15 minutes. The obtained micropowder was analyzed with an optical microscope, and the result was spherical composite particles 6 having a core-shell structure of a shell with a particle-like F polymer 1 as a core, and silica particles 1 attached to the surface of the core to form a shell. (D50: 3 μm).

，將光電子檢測角設為45度，將通過能量設為93.8 eV，將能階設為0.8 eV/step，將累計數設為16個循環。又，氟原子之含有比率係根據藉由測定所檢測出之各種峰強度(C1s、O1s、F1s及Si2s軌道)而算出。又，距離表面之深度係基於使用C60離子作為濺射離子之SiO₂ 濺射膜之濺射速率而決定。將各複合粒子之表面中之矽原子之量相對於氟原子之量(以下亦記為「Si/F量」)示於表3。2. Surface measurement of composite particles by ESCA When the surface was measured by ESCA, ESCA5500 manufactured by ULVAC-PHI was used. As for the X-ray source, monochromatic AlKα rays were used at 14 kV, an ion gun and a barium oxide emitter neutralization gun were used to prevent the electrification of the sample surface, and the photoelectron detection area was set to 800 μm

, the photoelectron detection angle was set to 45 degrees, the passing energy was set to 93.8 eV, the energy level was set to 0.8 eV/step, and the cumulative number was set to 16 cycles. In addition, the content ratio of a fluorine atom was calculated from the various peak intensities (C1s, O1s, F1s, and Si2s orbitals) detected by the measurement. In addition, the depth from the surface was determined based on the sputtering rate of the SiO ₂ sputtering film using C60 ions as sputtering ions. Table 3 shows the amount of silicon atoms in the surface of each composite particle relative to the amount of fluorine atoms (hereinafter also referred to as "Si/F amount").

3. Evaluation 3-1. Evaluation of dispersion stability The composite particles 6 and NMP were added to the container, and the container was stirred without adding a surfactant to prepare a liquid composition 1 in which the composite particles 6 were dispersed. The liquid composition 1 was left to stand for a predetermined time, and the dispersion stability thereof was evaluated according to the following criteria. [Evaluation Criteria] ○: Foaming was suppressed during preparation, and after preparation, even if it was left to stand at 25°C for 3 days, no precipitate was generated. Δ: Although foaming occurred during the preparation, even if it was left to stand at 25° C. for 3 days after preparation, no precipitate was generated. ×: Precipitates were generated when left to stand at 25°C for 3 days.

3-2. Evaluation of powder falling and warpage The liquid composition 1 was applied to the surface of a long copper foil (thickness: 18 μm) using a bar coater to form a liquid coating. Next, the copper foil on which the liquid coating was formed was passed into a drying furnace at 120° C. for 5 minutes, and dried by heating to obtain a dry coating. Then, the dried film was heated in a nitrogen oven at 380°C for 3 minutes. Thereby, the laminated body which has a copper foil, and the polymer layer which consists of the molten calcination of a polymer and a silicon dioxide located on the surface is obtained.

The powder fall of the dry coating and the warpage of the laminate were evaluated. The powder fall of the dry coating was visually confirmed at the edge of the dry coating, and evaluated according to the following criteria. [Evaluation criteria for falling powder] ○: No peeling was observed at the edge of the dry coating. △: Peeling was observed in a part of the edge of the dry coating. ×: Peeling was confirmed in a wide range of the edge portion of the dry coating.

The copper foil of the laminated body was removed by etching using an aqueous ferric chloride solution to produce a single polymer layer. A square test piece of 180 mm square was cut out from the polymer layer, and the test piece was measured by the measurement method specified in JIS C 6471:1995, and the evaluation was performed according to the following criteria. [Evaluation criteria for warpage] ○: The coefficient of linear expansion is less than ±20 ppm/°C. △: The linear expansion coefficient is ±20 ppm/°C or more and less than ±30 ppm/°C. ×: The linear expansion coefficient is ±30 ppm/°C or more. The above evaluation results are shown in Table 4.

[Example 3-2 to Example 3-5] The composite particles 7 to 10 were obtained in the same manner as in Example 3-1 except that the types and amounts of the particles were changed as shown in Table 1, and the composite particles 7 to 10 were used to prepare the liquid compositions 2 to 5. Moreover, the laminated body was obtained using the liquid compositions 2-5, respectively. Table 3 and Table 4 show the surface measurement results of the composite particles, the dispersion stability of each liquid composition, the powder falling of the dry coating, and the evaluation results of the warpage of the laminate.

[table 3] table 3 example 3-1 3-2 3-3 3-4 3-5 Composite particle number 6 7 8 9 10 F particles or PTFE particles F particle 1 (70) F particle 1 (70) F particle 4 (70) F particle 1 (90) PTFE2 (70) Silicon dioxide particle number 1(30) 2(30) 1(30) 1(10) 1(30) Si/F content 1.3 1.1 1.1 0.6 0.2 ※The value in parentheses is the content in each composite particle (unit: part by mass).

[Table 4] Table 4 example 3-1 3-2 3-3 3-4 3-5 Composite particle number 6 7 8 9 10 Liquid composition dispersion stability 〇 〇 △ △ × dry lamination powder 〇 △ △ × × Laminate warpage 〇 △ △ × × [Industrial Availability]

The dispersion liquid of the present invention has excellent dispersion stability, and can be easily processed into films, fiber-reinforced films, prepregs, and metal laminates (metal foils with resin). The obtained processed articles can be used as antenna parts, printed circuit boards, parts for aircraft, parts for automobiles, sports equipment, food industry supplies, sliding bearings and other materials. In addition, the composite particles of the present invention are excellent in handleability and dispersion stability in a dispersion medium. The liquid composition containing the composite particles of the present invention can be used for the production of molded articles (laminates, films, etc.) having properties based on F polymer and properties based on silica. The molded article formed from the composite particles of the present invention can be used as antenna parts, printed circuit boards, parts for aircrafts, parts for automobiles, sports equipment, food industry products, paints, cosmetics, etc. Specifically, it can be used as a wire coating material ( Aircraft wires, etc.), electrical insulating tapes, insulating tapes for oil drilling, materials for printed circuit boards, separation membranes (microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, ion exchange membranes, dialysis membranes, gas separation membranes, etc.), Electrode binders (for lithium secondary batteries, fuel cells, etc.), replica rolls, furniture, car dashboards, home appliances, etc. covers, sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belts) Conveyors, food conveying belts, etc.), tools (shovels, files, awls, saws, etc.), boilers, funnels, pipes, ovens, baking molds, chutes, eye molds, toilets, container coverings.

Claims (15)

A dispersion liquid comprising composite particles comprising a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an inorganic substance, an aromatic polymer, and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid dispersion medium, And the viscosity of the dispersion liquid at 25°C is 1000-100000 mPa·s. The dispersion liquid according to claim 1, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a perfluoro(alkyl vinyl ether)-based unit and having a polar functional group, or is a tetrafluoroethylene-based polymer containing a unit based on a perfluoro(alkyl vinyl ether) and having a polar functional group, or a 2.0-5.0 mol % of tetrafluoroethylene-based polymers based on perfluoro(alkyl vinyl ether) units and not having polar functional groups. The dispersion liquid of claim 1 or 2, wherein the inorganic substance is silicon dioxide. The dispersion liquid according to any one of claims 1 to 3, wherein the content of the above-mentioned aromatic polymer is less than the content of the above-mentioned composite particles. The dispersion liquid according to any one of claims 1 to 4, wherein the aromatic polymer is selected from the group consisting of aromatic polyimide, aromatic polyamide, aromatic polyamide imide, polyphenylene ether, liquid crystal At least one of the group consisting of polyester and aromatic maleimide. A dispersion liquid containing composite particles comprising a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and an inorganic substance, and a liquid dispersion medium, wherein the composite particles are dispersed in the liquid dispersion medium, and the liquid dispersion The medium includes two liquid dispersion media having different boiling points, and the two liquid dispersion media are in a relationship of forming an azeotrope. The dispersion liquid according to claim 6, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer containing a perfluoro(alkyl vinyl ether)-based unit and having a polar functional group, or is a tetrafluoroethylene-based polymer containing a polar functional group relative to the total unit 2.0-5.0 mol % of tetrafluoroethylene-based polymers based on perfluoro(alkyl vinyl ether) units and not having polar functional groups. The dispersion liquid of claim 6 or 7, wherein the mixing ratio of the high-boiling-point dispersion medium in the above-mentioned two liquid dispersion media with different boiling points is more than that of the high-boiling-point dispersion medium in the azeotropic mixture of the above-mentioned two liquid dispersion media The composition ratio (mass ratio). The dispersion liquid according to any one of claims 6 to 8, wherein at least one of the two liquid dispersion media having different boiling points constituting the above-mentioned liquid dispersion medium is water, alcohol or amide. A composite particle containing a tetrafluoroethylene-based polymer having a melting temperature of 260 to 320° C. and containing 1 to 5 mol % of perfluoro(alkyl vinyl ether)-based units with respect to the total units, and silica , the amount of silicon atoms on the surface measured by X-ray photoelectron spectroscopy is 1 or more relative to the amount of fluorine atoms. The composite particles according to claim 10 have an average particle diameter of 2 μm or more and 10 μm or less. The composite particle according to claim 10 or 11, wherein the amount of the silica is 15 to 85 parts by mass relative to 100 parts by mass of the tetrafluoroethylene-based polymer. The composite particle according to any one of claims 10 to 12, wherein the above-mentioned tetrafluoroethylene-based polymer is used as a core, and the above-mentioned silica is provided on the surface of the above-mentioned core. The composite particle according to any one of claims 10 to 13, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having a polar functional group. A method for producing composite particles, the composite particles being the composite particles according to any one of Claims 10 to 14, wherein the method for producing the composite particles comprises mixing the particles of the tetrafluoroethylene-based polymer with the silica in the four The above-mentioned composite particles are obtained by colliding in a suspended state at a temperature higher than the melting temperature of the vinyl fluoride-based polymer.